CL-SR (O) N-Ts Synthesis Method 2

Supporting Information
Rapid Deoxyfluorination of Alcohols with N-Tosyl-4-

chlorobenzenesulfonimidoyl Fluoride (SulfoxFluor) at Room
Temperature
Junkai Guo, Cuiwen Kuang, Jian Rong, Lingchun Li, Chuanfa Ni,* and Jinbo Hu*[a]
chem_201901176_sm_miscellaneous_information.pdf
Table of Contents
1. General Information ...........................................................................................S-2

2. Screening of Reaction Conditions ......................................................................S-3
3. Preparation of SulfoxFluor (1a) and Other Sulfonimidoyl Fluorides ..........S-13
4. Synthesis of Alcohols…………………………………………………………..S-22
5. Deoxyfluorination of Alcohols 2 with SulfoxFluor (1a)……………………..S-30
6. Deoxyfluorination of Multiple Alcohols 6 with SulfoxFluor (1a)………..…S-46
7. Gram-Scale Deoxyfluorination of Alcohol 2n with SulfoxFluor (1a)………S-53
8. Mass Balance Analysis of the Deoxyfluorination of Primary Alcohols...…. S-54
9. Recovery of Deoxyfluorination Byproduct………..………………………….S-57
10. Mechanistic Investigation on the Deoxyfluorination of Alcohols with
SulfoxFluor (1a)………………………………………………………………….S-59
11. References……………………………...……………………………………..S-65
12. NMR Spectra……………………...………………………………………….S-67
S-1
1. General Information
Unless otherwise mentioned, solvents and reagents were purchased from
commercial sources and used as received. Toluene, acetonitrile (CH3CN),
tetrahydrofuran (THF), dichloromethane (CH2Cl2), N,N-dimethylformamide (DMF),
dimethyl sulfoxide (DMSO), diethyl ether (Et2O), 1,4-dioxane, 1,2-dimethoxyethane
(DME) were dispensed from a dry solvent system. Tetrabutylammonium
tetra(tert-butanol) coordinated fluoride [TBAF(tBuOH)4]1 and PyFluor2 were
prepared as per reported procedures. 1H, 13C and 19F NMR spectra were recorded on a
500 MHz or 400 MHz NMR spectrometer. 1H NMR chemical shifts were determined
relative to internal (CH3)4Si (TMS) at δ 0.0 or to the signal of the residual protonated
13
solvent: CDCl3 δ = 7.26 ppm, CD3OD δ = 3.31 ppm, DMSO-d6 δ = 2.50 ppm. C
19
NMR chemical shifts were determined relative to internal TMS at δ 0.0. F NMR
chemical shifts were determined relative to CFCl3 at δ 0.0. Data for 1H, 13
C and 19
F
NMR are recorded as follows: chemical shift (δ, ppm), multiplicity (s = singlet, d =
doublet, t = triplet, m = multiplet, q = quartet, br = broad). Mass spactra were
obtained on a mass spectrometer. High-resolution mass data were recorded on a
high-resolution mass spectrometer in the EI or ESI mode.
S-2
2. Screening of Reaction Conditions
2.1. Deoxyfluorination of Secondary Alcohols.
Table S1. The reaction of secondary alcohols: Screening the basesa
O NTs OH F
S base (1.1equiv)
F +
toluene (0.1 M)
rt, 12 h
1b 2a 3a
(1.1 equiv) (0.2 mmol)
Entry Base Yield (%)b
1 DBU 59
2 MTBD 33
3 TBD 34
4 TMG 13
5 N,N-diisopropylethylamine 0
6 DMAP 0
7 DABCO 0
8 4-pyrrolidinopyridine 0
9 Et3N 0
10 pyridine 0
a
Reactions were perfomed on 0.2-mmol scale in a polytetrafluoroethene (PTFE) tube.
b
Yields of 3a were determined by 19F NMR analysis using 1-fluoronaphthalene as an
internal standard.
N N NH
N N N N N N
H
MTBD TBD TMG
Typical Experimental Procedures (Table S1, entry 1):

A 25-mL polytetrafluoroethylene (PTFE) tube was charged sequentially with
4-phenylbutan-2-ol (2a) (30.0 mg, 0.20 mmol), N-tosylbenzenesulfonimidoyl fluoride
(1b) (68.9 mg, 0.22 mmol) in toluene (2.0 mL), and finally DBU (36 μL, 0.22 mmol)
was added under N2 atmosphere. After stirring at 600 rpm for 12 hours,
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1-fluoronaphthalene (25 μL, 0.19 mmol) was added as an internal standard. The yield
of (3-fluorobutyl)benzene (3a) was determined by 19F NMR spectroscopy analysis.
Summary of Results:
The results showed that DBU was the optimal base.
Table S2. The reaction of secondary alcohols: Screening the sulfonimidoyl fluorides.a
OH F
Sulfonimidoyl fluoride (1.1 equiv)
DBU (1.1 equiv)

2a toluene (0.1 M) 3a
(0.2 mmol) rt, 12 h
Entry Sulfonimidoyl fluoride Yield (%)b 3a/alkenec
O NTs
S
1 F (1b) 53 10:1
O NTs
S
F 74 20:1
2
Cl (SulfoxFluor, 1a)
O NTs
S
F
3 56 7:1
(1c)
O2N
O NBz
S
4 F 52 6:1
(1d)
Cl
F O
S
5 N (1e) 0 NDd
Ph CF2SO2Ph
a
Reactions were perfomed on 0.2-mmol scale in a PTFE tube following similar
procedures as described for Table S1. bYields of 3a were determined by 19F
NMR analysis using 1-fluoronaphthalene as an internal standard. cDetermined
by GC-MS analysis. dNot determined.
Summary of Results:
S-4
The results showed that the electronic nature of the substituents on both the sulfur
atom and the nitrogen atom of a sulfonimidoyl fluoride could significantly influence
the yield of the fluorination product 3a, with SulfoxFluor (1a) being the most
effective.
Table S3. The reaction of secondary alcohols: Screening the equivalents of DBU.a
Summary of Results:
The results showed that the use of 1.5–1.8 equiv of DBU was optimal for the
deoxyfluorination of secondary alcohols..
S-5
Table S4. The reaction of secondary alcohols: Screening the reaction time.a
O NTs OH F
S DBU (1.5 equiv)
F +
Cl toluene (0.1 M)
SulfoxFluor (1a) 2a rt, time 3a
(1.1 equiv) (0.2 mmol)
Entry Time (min) Yield (%)b
1 0 0
2 1 5
3 2 17
4 5 41
5 10 49
6 15 54
7 20 58
8 30 68
9 60 68
a
Reactions were perfomed on 0.2-mmol scale in a PTFE tube following similar procedures
as described for Table S1. bYields of 3a were determined by 19F NMR analysis using 1-
fluoronaphthalene as an internal standard.
Summary of Results:
The deoxyfluorination of secondary alcohols with SulfoxFluor (1a) (1.1 equiv)
and DBU (1.5 equiv) was completed in 30 minutes. Therfore, we chose 30 minutues
as the reaction time and further optimized the reactant ratio.
S-6
Table S5. The reaction of secondary alcohols: Further screening the reactant ratios.
Summary of Results:
A further screening of the reaction conditions showed that the highest yield of
74% (19F NMR yield) could also be obtained in 30 min by performing the reaction
with 1.2 equiv of SulfoxFluor (1a) and 1.6 equiv of DBU.
S-7
Table S6. The reaction of secondary alcohols: Comparison with Sulfonyl Fluorides.a
OH F
Reagent (1.2 equiv), DBU (1.6 equiv)
toluene (0.1 M), rt, 30 min

2a 3a
(0.2 mmol)
Entry Reagent Yield (%)b 3a/alkenec
O NTs
S
F 74 22:1
1
Cl (SulfoxFluor, 1a)
O O
S
F
2 <5 NDd
N (PyFluor)
F F FO O
F
S
3 F F 62 9:1
F F F F (PBSF)
a
Reactions were perfomed on 0.2-mmol scale in a PTFE tube following similar
procedures as described for Table S1. bYields of 3a were determined by 19F
NMR analysis using 1-fluoronaphthalene as an internal standard. cDetermined
by GC-MS analysis. dNot determined.
Summary of Results:
In the case of PyFluor, a stirring of the reaction mixture at room temperature for
30 min afforded only trace amount of 3a (Table 1, entry 8), a result similar to
previous report.2 When PBSF was used instead of SulfoxFluor (1a), although the
reaction could be finished in 30 min, it afforded a little lower yield of 3a (62%) and
relatively high yield of the elimination product 3a’. Despite its comparable reactivity,
the high fluorine content of PBSF renders it fall short of the concept of fluorine
economy. Obviously, SulfoxFluor (1a) is more suitable for both fluorine economical
and rapid deoxyfluorination of alcohols.
S-8
2.2. Deoxyfluorination of Primary Alcohols.
Table S7. The reaction of primary alcohols: Influence of the reaction vessel.a
Experimental Procedures:
A 25-mL Schlenk tube (glass) or 10-mL polytetrafluoroethylene (PTFE) tube was
charged sequentially with 2-naphthaleneethanol (2t) (34.4 mg, 0.2 mmol),
N-tosylbenzenesulfonimidoyl fluoride (1b) (68.9 mg, 0.22 mmol) in toluene (2.0 mL),
and finally DBU (33 μL, 0.22 mmol) was added. After stirring at 600 rpm for 12
hours, 1-fluoronaphthalene (25 μL, 0.19 mmol) was added as an internal standard, and
19
the yield of 1-(2-fluoroethyl)naphthalene (3t) was determined by F NMR
spectroscopy analysis.
Summary of Results:
Considering that DBU-HF complex was formed during the reaction, we
investigated the influence of the material of the reaction veseel (glass vs PTFE).
Results showed that the reaction performed in a PTFE vessel gave higher yield of the
desired fluorination products. The decrease of the yield in a glass vessel is attributed
to the consumption of some HF by glass. A vessel made of HDPE (high density
polyethylene) can be used instead of a PTFE vessel.
S-9
Table S8. The reaction of primary alcohols: Screening the reaction time.a

2-naphthaleneethanol (2t) (34.4 mg, 0.2 mmol), SulfoxFluor (1a) (76.5 mg, 0.22
mmol) in toluene (2.0 mL), and finally DBU (33 μL, 0.22 mmol) was added. After
stirring at 600 rpm for 10 min, 1-fluoronaphthalene (25 μL, 0.19 mmol) was added as
an internal standard, and the yield of 1-(2-fluoroethyl)naphthalene (3t) was
determined by 19F NMR spectroscopy analysis.
Summary of Results:
The deoxyfluorination of primary alcohols with SulfoxFluor (1a) (1.1 equiv) and
DBU (1.1 equiv) was nearly completed in 10 minutes. Therfore, we chose 10
minutues as the reaction time and further optimized the reactant ratio.
S-10
Table S9. The reaction of primary alcohols: Screening the reactant ratios.a
Summary of Results:
A further screening of the reaction conditions showed that the desired fluorination
product 1-(2-fluoroethyl)naphthalene (3t) could be produced in higher yield (78%
based on 19F NMR) when slightly more excess SulfoxFluor (1a) and DBU were used
(Table S9, entry 2). The reaction performed in an HDPE (high density polyethylene)
tube gave similar result (Table S9, entry 3). However, much more excess SulfoxFluor
(1a) and DBU could not further improve the yield of 3t (Table S9, entry 4), probabaly
due to the increasing competitive N-alkylation of DBU.
S-11
Table S10. The reaction of primary alcohols: Screening the external fluorides.a
O NTs DBU (1.2 equiv)

OH S external fluoride F
+ F
Cl toluene (0.1 M)
2t SulfoxFluor (1a) 3t
(0.2 mmol) (1.2 equiv)
Entry External fluoride Equivalents Yield (%)b
1 None - 79 (79)
2 CsF 1.0 53
c .
3 Et3N 3HF 1.0 8
4d Et3N.3HF 0.3 68
5 TBAT 0.5 79
6 TBAT 1.0 83
7 TBAT 2.0 76
8 TBAF(tBuOH)4 0.5 83
9 TBAF(tBuOH)4 1.0 92 (86)
10 TBAF(tBuOH)4 2.0 85
11 TBAF (1 M in THF) 2.0 33
a
Reactions were perfomed on 0.2-mmol scale in a PTFE tube. bYields of 3t were determined by 19F
NMR analysis using 1-fluoronaphthalene as an internal standard. Isolated yields are given in the
parentheses. cEt3N.3HF was finally added. d Et3N.3HF and DBU were added first, and the mixture
was stirred for 10 min before the addition of other reactants.

2-naphthaleneethanol (2t) (34.4 mg, 0.2 mmol), SulfoxFluor (1a) (83.4 mg, 0.24
mmol), toluene (2 mL), TBAF(tBuOH)4 (110 mg, 0.2 mmol) and DBU (36 μL, 0.24
mmol). After stirring under the protection of N2 at 600 rpm at room temperature for 30
minutes, 1-fluoronaphthalene (25 μL, 0.19 mmol) was added as an internal standard,
19
and the yield of 1-(2-fluoroethyl)naphthalene (3t) was determined by F NMR
spectroscopy analysis.
Summary of Results:
In the deoxyfluorination of primary alcohol 2t, the N-alkylation of DBU can
significantly decrease the yield of the desired fluorination product 3t. It was found
that the addition of an external source can promote the desired fluorination, thus
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improving the yield of alkyl fluoride 3t. Among various fluoride sources examined,
TBAF(tBuOH)4 was found to be the most effective due to its good solubility, low
hygroscopicity, as well as good nucleophilicity with low basicity (Ref.: Kim, D. W.
Jeong, H.-J. Lim, S. T. Sohn, M.-H. Angew. Chem., Int. Ed. 2008, 47, 8404).
3. Preparation of SulfoxFluor (1a) and Other
Sulfonimidoyl Fluorides
3.1. Preparation of SulfoxFluor (1a)
3.1.1. Preparation of N-Tosyl-4-chlorobenzenesulfonimidoyl Chloride (5)
The corresponding sulfonimidoyl chloride 5 was prepared from commericially
available 4-chlorobenzenesulfonyl chloride by a modification of reported
procedures.3,4
Reduction of 4-chlorobenzenesulfonyl chloride. A 1-L flask was charged with
4-chlorobenzenesulfonyl chloride (4) (42.20 g, 200 mmol) and water (600 mL). Then
sodium sulfite (40.32 g, 320 mmol, 1.6 equiv) and sodium bicarbonate (26.90 g, 320
mmol, 1.6 equiv) were added, and the reaction mixture was refluxed for 3 hours. After
the evaporation of water under vacuum, ethanol (500 mL) was added to the residue.
The so-obtained suspension was heated at 60 oC for 10 minutes to dissolve sodium
4-chlorobenzenesulfinate, cooled, and filtered. This was repeated twice with the
residue from the filtration. The ethanol fractions were combined, and the solvent was
evaporated under vacuum, and the crude sodium 4-chlorobenzenesulfinate was
isolated as white powders, and used without further purification.
Chlorination of sodium 4-chlorobenzenesulfinate. A 1-L three-necked flask
connected with an SO2 absorption apparatus was charged with the crude sodium
4-chlorobenzenesulfinate and dichloromethane (500 mL). The reaction mixture was
S-13
cooled to 0 oC, then thionyl chloride (43.2 mL, 600 mmol) was added slowly (in 30
minutes) while stirring vigorously. After the complete addition of thionyl chloride, the
mixture was stirred at 0 oC for 30 minutes, then was warmed to 23 oC and stirred at
this temperature for 3 hours. After removal of solids through filtration, the solution
was concentrated to afford crude 4-chlorobenzenesulfinyl chloride as a light yellow
liquid.
S-Imination of 4-chlorobenzenesulfinyl chloride. The crude
4-chlorobenzenesulfinyl chloride was immediately added to a 1-L flask containing
anhydrous chloramine T (40.95 g, 180 mmol) and toluene (500 mL). The resulting
suspension was heated at 80 oC for 3 h while stirring vigorously. After cooling, the
solids were filtered off and washed with toluene. The filtrate was evaporated in vacuo
to give a crystalline residue. Recrystallization from ethyl acetate/petroleum ether
afforded 5 as white solids (38.10 g). The mother liquid was concentrated and purified
by a silica gel column chromatography with petroleum ether/ethyl acetate (20:1, v/v)
as the eluent to give a second portion of 5 as white solids (1.64 g). The total yield of 5
was 61% (39.74 g).
Melting point: 90–92 oC. 1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.9 Hz, 2H),
7.95 (d, J = 8.3 Hz, 2H), 7.58 (d, J = 8.9 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 2.44 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 144.13, 142.86, 140.95, 138.27, 130.27, 129.88,
128.45, 127.60, 21.81. IR (thin film): 3098, 3035, 2955, 2923, 1933, 1917, 1595,
1573, 1397, 1335, 1288, 1278, 1162, 1119, 1085, 830, 819, 733, 559, 548 cm–1. MS
(EI, m/z, %): 363 (M+, 0.83), 91 (100.00); HRMS (EI): Calcd. For C13H11NO3S2Cl2+:
362.9552; Found: 362.9562.
3.1.2 F-Cl Exchange for Preparing SulfoxFluor (1a)
SulfoxFluor
O NTs 18-crown-6 (1 mol%) O NTs
S S
Cl KF (2 equiv) F
Cl CH3CN, rt, 1 d Cl
5 80% SulfoxFluor (1a)
S-14
N-Tosyl-4-chlorobenzenesulfonimidoyl fluoride (SulfoxFluor, 1a) was prepared
from 5 according to reported procudures.4
Under argon atomosphere, to a solution of
N-tosyl-4-chlorobenzenesulfonimidoyl chloride (5) (39.7 g, 109 mmol) in dry
acetonitrile (500 mL) were added anhydrous potassium fluoride (12.7 g, 218 mmol,
2.0 equiv) and 18-crown-6 (288.0 mg, 1.09 mmol, 1 mol%). The resulting suspension
was stirred vigorously at room temperature for 1 day, and then kept still for 30
minutes to allow the precipitation of the amorphous solids. After filtration, the filtrate
was evaporated in vacuo to give a crystalline residue. Recrystallization from ethyl
acetate/petroleum ether afforded 19.97 g of 1a as white solids. The mother liquid was
concentrated and purified by a silica gel column chromatography with petroleum
ether/ethyl acetate (10:1 to 5:1, v/v) as the eluent to give a second portion of 1a as
white solids (10.48 g). The total yield of SulfoxFluor (1a) was 80% (30.45 g).
7.92 (d, J = 8.3 Hz, 2H), 7.59 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 8.4 Hz, 2H), 2.43 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 144.65, 143.51, 138.72, 131.50 (d, J = 21.7 Hz),
130.29, 129.83, 129.59, 127.20, 21.76. 19F NMR (376 MHz, CDCl3): δ 74.07 (s). IR
(thin film): 3100, 3037, 2958, 2923, 1936, 1783, 1595, 1576, 1473, 1401, 1337, 1324,
1186, 1158, 1087, 1011, 787, 707, 648, 552 cm–1. MS (EI, m/z, %): 347 (M+, 4.23),
220 (100.00); HRMS (EI): Calcd. For C13H11NO3FS2Cl+: 346.9847; Found: 346.9854.
S-15
X-ray Crystal Structure Analysis of SulfoxFluor (1a)
Figure S1. The ORTEP diagram of the crystal structure of SulfoxFluor (1a).
Table S11. Crystal data and structure refinement for SulfoxFluor (1a).
Empirical formula C13H11ClFNO3S2

Formula weight 347.80
Temperature 293(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group P 21/n
Unit cell dimensions a = 7.9718(11) Å a= 90o
b = 14.884(2) Å b= 95.817(3)o
c = 12.4865(18) Å g = 90o
Volume 1474.0(4) Å3
Z 4
Density (calculated) 1.567 Mg/m3
Absorption coefficient 0.561 mm-1
F(000) 712
Crystal size 0.200 x 0.170 x 0.130 mm3
Theta range for data collection 2.135 to 25.997o
Index ranges -9<=h<=9, -18<=k<=17, -15<=l<=11
Reflections collected 8701
S-16
Independent reflections 2893 [R(int) = 0.0333]
Completeness to theta = 25.242o 100.0 %
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.7456 and 0.6011
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 2893 / 0 / 191
Goodness-of-fit on F2 1.049
Final R indices [I>2sigma(I)] R1 = 0.0427, wR2 = 0.1159
R indices (all data) R1 = 0.0514, wR2 = 0.1218
Extinction coefficient n/a
Largest diff. peak and hole 0.457 and -0.202 e.Å-3
DSC Thermal Analysis of SulfoxFluor (1a)
The thermal stability of SulfoxFluor (1a) was evaluated using Differential

Scanning Calorimetry (DSC) analysis. A sample of 1a (2.000 mg) was sealed in a
crimped hermetic pan under ambient air and was subjected to a gradient of 0–350 oC at
a rate of 5 oC/min. No exothermic decomposition is observed in the range of 0–330 oC.
The endotherms of −99 J/g at 102 oC and −301 J/g at 260 oC correspond to melting and
evaporation of 1a.
S-17
Figure S2. DSC Thermal Analysis of SulfoxFluor (1a)
3.2. Preparation of N-Tosylbenzenesulfonimidoyl Fluoride (1b)
N-Tosylbenzenesulfonimidoyl fluoride (1b) was prepared similarly to 1a except
that the commericially available PhSO2Na was used as the starting material.
The intermediate N-tosylbenzenesulfonimidoyl chloride (S1) was prepared from
PhSO2Na (8.30 g, 50.0 mmol), and obtained as a white solid in 52% yield (7.09 g). 1H
NMR (400 MHz, CDCl3) δ 8.06 (d, J = 8.3 Hz, 2H), 7.97 (d, J = 8.2 Hz, 2H), 7.75 (t,
J = 7.5 Hz, 1H), 7.62 (t, J = 7.9 Hz, 2H), 7.35 (d, J = 8.5 Hz, 2H), 2.45 (s, 3H). The
characterization data are in agreement with the literature.4
S-18
N-Tosylbenzenesulfonimidoyl fluoride (1b) was prepared from S1 as a white solid
in 81% yield (5.39 g). 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 7.7 Hz, 2H), 7.95 (d,
J = 8.4 Hz, 2H), 7.79 (t, J = 7.5 Hz, 1H), 7.62 (t, J = 7.9 Hz, 2H), 7.34 (d, J = 8.5 Hz,
19
2H), 2.44 (s, 3H). F NMR (376 MHz, CDCl3) δ 73.72(s, 1F). The characterization
data are in agreement with the literature.4
3.3. Preparation of N-Tosyl-4-nitrobenzenesulfonimidoyl Fluoride
(1c)
4-Nitrobenzenesulfinyl chloride (S2) was prepared from 4-nitrobenzenethiol
according to reported procedures.5 After removal of the volatile materials in vacuum,
the so-obtained crude product S2 was used directly for next step.
N-Tosyl-4-nitrobenzenesulfonimidoyl chloride (S3) was prepared from the crude
S2 and chloroamine-T using procedures similar to those described for the preparation
of 5 from crude 4-chlorobenzenesulfinyl chloride. In this case, the crude product S3
was used directly for next step.
N-Tosyl-4-nitrobenzenesulfonimidoyl fluoride (1c) was prepared from crude S3
using procedures similar to those described for the preparation of 1a from 5.
Starting from 4-nitrobenzenethiol (3.875 g, 25.0 mmol), the title compound 1c
was obtained as a white solid in 10% overall yield (896 mg). Melting point: 108–111
o
C. 1H NMR (400 MHz, CDCl3) δ 8.46 (d, J = 8.8 Hz, 2H), 8.27 (d, J = 9.0 Hz, 2H),
S-19
7.94 (d, J = 8.3 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 2.46 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 152.04, 145.04, 138.68 (d, J = 23.0 Hz), 138.35, 129.95, 129.77, 127.21,
19
125.02, 21.74. F NMR (376 MHz, CDCl3) δ 74.00 (s, 1F). IR (thin film): 3112,
3069, 2922, 2853, 1923, 1609, 1598, 1533, 1408, 1343, 1307, 1185, 1154, 1088, 1012,
856, 778, 695, 544 cm–1. MS (EI, m/z, %): 358 (M+, 10.39), 91 (100.00); HRMS (EI):
Calcd. For C13H11N2O5FS2+: 358.0088; Found: 358.0100.
3.4. Preparation of N-Benzoyl-4-chlorobenzenesulfonimidoyl
Fluoride (1d)
N-Benzoyl-4-chlorobenzenesulfonimidoyl fluoride (1d) was prepared from
sodium 4-chlorobenzenesulfinate according to reported procedures.4
N-((4-Chlorophenyl)sulfinyl)benzamide (S4)
White solide. 1 H NMR (400 MHz, CDCl3 ) δ 8.29 (s, 1H), 7.80 (d, J = 7.2 Hz,
2H), 7.73 (d, J = 8.6 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H), 7.54 (d, J = 8.6 Hz, 2H),
7.46 (t, J = 7.7 Hz, 2H). The characterization data are in agreement with the
literature.4
N-Benzoyl-4-chlorobenzenesulfonimidoyl Fluoride (1d)
White solide. 1H NMR (400 MHz, CDCl3) δ 8.15–8.12 (m, 4H), 7.65 (d, J = 8.8
19
Hz, 2H), 7.58 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.8 Hz, 2H). F NMR (376 MHz,
CDCl3) δ 65.78 (s, 1F). The characterization data are in agreement with the literature.4
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3.5. Preparation of
(1S,3R)-3-(Difluoro(phenylsulfonyl)methyl)-1-fluoro-3-phenylbenzo[d] isothi-
azole 1-oxide (1e)
A 25-mL Schlenk tube was charged sequentially with
(1R,3R)-3-(difluoro(phenylsulfonyl)methyl)-3-phenyl-2,3-dihydrobenzo[d]isothiazole
1-oxide (S5)6 (209.5 mg, 0.5 mmol, 1.0 equiv), Selectfluor (195.0 mg, 0.55 mmol, 1.1
equiv) and CH3CN (4 mL). The mixture was stirred at room temperature for 12 hours.
After the addition of water (5 mL), the mixture was extracted with Et2O (3 × 5 mL),
dried over Na2SO4, evaporated under vacuum, and purified by silica gel column
chromatography (petroleum ether/ethyl acetate, 4:1, v/v) to give the title compound 1e
as a white solid (167.5 mg, 81% yield).
Melting point: 172–175 oC. 1H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 7.6 Hz,
1H), 7.92–7.85 (m, 5H), 7.78 (t, J = 7.5 Hz, 1H), 7.69 (q, J = 8.0 Hz, 2H), 7.54 (t, J =
19
7.5 Hz, 2H), 7.37 (s, 3H). F NMR (376 MHz, CDCl3) δ 80.75 (d, J = 9.0 Hz, 1F),
–99.02 (m, 2F). 13C NMR (125 MHz, CDCl3) δ 146.60, 135.90, 135.63 (d, J = 8.4 Hz),
135.26, 135.12, 134.80, 131.17, 131.03, 129.62 (t, J = 10.2 Hz), 129.44, 129.25,
128.97, 128.66, 127.14, 127.02, 126.99 (d, J = 0.8 Hz), 75.78 (dt, J = 22.7, 3.8 H). IR
(thin film): 3062, 1581, 1459, 1447, 1171, 1133, 1094, 1002, 758, 717, 607, 571, 541
cm–1.
S-21
4. Synthesis of Alcohols
Alcohols 2h-2k, 2q-2v, 2t, and 4c were commercially available. Alcohols 2b-2g,7
2l-2p,7 2w, 8 6a7 were synthesized according to previous reports. Procedures for the
synthesis of alcohols 6b and 6d-6j are described as follows:
4.1. 3α-Hydroxy-5β-cholan-24-ol (6b)
S-22
3α-Hydroxy-5β-cholan-24-ol (6b) was prepared according to previuos report.9
Under argon atomosphere, a dry 250-mL round bottomed flask was charged with
LiAlH4 (364 mg, 9.6 mmol, 3.0 equiv), magnetic stir bar, and freshly distilled
tetrahydrofuran (27 mL). Lithocholic acid (1.2053 g, 3.2 mmol, 1.0 equiv) dissolved
in tetrahydrofuran (27 mL) was then added to the stirring LiAlH4 suspension cooled
to 0 oC. The reaction mixture was refluxed for 2 hours, then another portion of LiAlH4
(57 mg, 1.5 mmol, 0.5 equiv) was added. After an additional 85 minutes the reaction
was cooled to 0 oC and 1N HCl was added dropwise until effervescence ceased. The
acidified mixture was transferred to a separatory funnel, extracted with diethyl ether
(3 × 50 mL). The combined organic extracts were dried over Na2SO4, and
concentrated in vacuo to give 3α-hydroxy-5β-cholan-24-ol (6b) as a white crystalline
solid (1.1000 g, 95% yield).
1
H NMR (500 MHz, CD3OD) δ 4.86 (s, 2H), 3.57–3.47 (m, 3H), 2.03 (dt, J =
12.5, 3.0 Hz, 1H), 1.95–1.86 (m, 2H), 1.85–1.73 (m, 2H), 1.65–1.57 (m, 3H),
1.51–1.36 (m, 9H), 1.34–1.24 (m, 4H), 1.21–1.06 (m, 6H), 1.03–0.95 (m, 7H), 0.70 (s,
3H). 13C NMR (100 MHz, CD3OD) δ 72.42, 63.57, 57.96, 57.69, 43.87, 43.55, 41.90,
41.58, 37.25, 37.18, 36.99, 36.50, 35.69, 33.20, 31.20, 30.29, 29.34, 28.38, 27.68,
25.29, 23.97, 21.97, 19.20, 12.52. The characterization data are in agreement with
previuos report.10
4.2. 6-Phenethyl-8-phenyloctane-1,6-diol (6d)
6-Phenethyl-8-phenyloctane-1,6-diol (6d) was prepared according to reference
with modification.11 The following procedure was almost the same with that of 2c7
S-23
o
except oxepan-2-one was added at 0 C and adding no CuI. Starting from
oxepan-2-one (1.39g, 12.2 mmol), the title compound 6d was obtained as as a white
solid (3.5 g, 88% yield).
Melting point: 35–37 oC. 1H NMR (400 MHz, CDCl3) δ 7.29–7.25 (m, 4H),
7.19–7.15 (m, 6H), 3.61 (t, J = 6.6 Hz, 2H), 2.67–2.62 (m, 4H), 2.19 (s, 2H),
1.82–1.77 (m, 4H), 1.58–1.54 (m, 4H), 1.37 (s, 4H). 13C NMR (100 MHz, CDCl3) δ
156.94, 134.36, 129.28, 114.46, 67.39, 65.67, 60.20, 41.01, 32.03, 31.18, 23.52. IR
(thin film): 3421, 3024, 2937, 2862, 1601, 1496, 1453, 1046, 754, 700 cm–1. MS (EI,
m/z, %): 308 (M+, 4.24), 91 (100.00); HRMS (EI): Calcd. For C22H28O+: 308.2135;
Found: 308.2135.
4.3. 4-(4-(3-Hydroxypropoxy)phenyl)cyclohexanol (6e)
4-(4-(3-Hydroxypropoxy)phenyl)cyclohexanone (S6) was prepared according to
previous report.12 4-(4-(3-Hydroxypropoxy)phenyl)cyclohexanone (1.90 g, 10 mmol,
1.0 equiv) was dissolved in acetone (20 mL) and 3-bromopropan-1-ol (1.38 g, 10
mmol, 1 equiv), potassium carbonate (1.38 g, 10 mmol, 1 equiv) were sequentially
added. The reaction mixture was heated at 60 oC for 12 h. After cooling, the solid was
filtered off and water was added and the mixture was extracted with EtOAc (2 × 50
mL). The combined organic extracts were dried (Na2SO4), concentrated under
reduced pressure, and purified by column chromatography on silica gel (petroleum
ether/EtOAc 2:1, v/v) to give S6 as a white solid (1.59 g, 64% yield).
S-24
6.86 (d, J = 8.7 Hz, 2H), 4.10 (t, J = 6.0 Hz, 2H), 3.84 (t, J = 5.9 Hz, 2H), 2.97 (tt, J =
12.1, 3.3 Hz, 1H), 2.50–2.44 (m, 4H), 2.20–2.15 (m, 2H), 2.12 (s, 1H), 2.03 (p, J =
13
5.9 Hz, 2H), 1.88 (ddd, J = 18.0, 12.3, 6.5 Hz, 2H). C NMR (100 MHz, CDCl3) δ
211.38, 157.45, 137.11, 127.59, 114.59, 65.76, 60.38, 41.90, 41.36, 34.17, 32.04. IR
(thin film): 3393, 3063, 2939, 2922, 2876, 1714, 1613, 1518, 1251, 1042, 991, 842,
812, 546, 502 cm–1. MS (EI, m/z, %): 248 (M+, 76.63), 133 (100.00); HRMS (EI):
Calcd. For C15H20O3+: 248.1407; Found: 248.1417.
4-(4-(3-Hydroxypropoxy)phenyl)cyclohexanol (6e) was prepared according to
reference.13 4-(4-(3-Hydroxypropoxy)phenyl)cyclohexanone (S6) (1.50 g, 6.0 mmol,
1 equiv) was dissolved in EtOH (20 mL) and cooled to 0 oC, then NaBH4 (229 mg,
6.0 mmol, 1 equiv) was added. The reaction mixture was stirred at 0 oC for 30
minutes and then warmed to room temperature and stirred for 12 hours. After the
addition of water (25 mL), the mixture was extracted with EtOAc (2 × 50 mL). The
combined organic phases were dried (Na2SO4), concentrated under reduced pressure,
and purified by column chromatography on silica gel (petroleum ether/EtOAc 1:2,
v/v) to afford 4-(4-(3-hydroxypropoxy)phenyl)cyclohexanol (6e) as a white solid
(1.21 g, 93% yield).
Melting point: 137–138 oC. 1H NMR (500 MHz, CD3OD) δ 7.09 (d, J = 8.6 Hz,
2H), 6.82 (d, J = 8.6 Hz, 2H), 4.86 (s, 2H), 4.03 (t, J = 6.3 Hz, 2H), 3.73 (t, J = 6.3 Hz,
2H), 3.61–3.55 (m, 1H), 2.41 (tt, J = 12.0, 3.3 Hz, 1H), 2.04–2.01 (m, 2H), 1.96 (p, J
13
= 6.3 Hz, 2H), 1.85–1.82 (m, 2H), 1.53–1.35 (m, 4H). C NMR (100 MHz,
DMSO-d6) δ 156.8, 138.66, 127.45, 114.15, 68.70, 64.44, 57.35, 42.10, 35.83, 32.51,
32.18. IR (thin film): 3385, 3038, 2924, 2871, 1610, 1515, 1471, 1243, 1062, 840,
811, 547 cm–1. MS (EI, m/z, %): 250 (M+, 77.92), 232 (100.00); HRMS (EI): Calcd.
For C15H22O3+: 250.1563; Found: 250.1570.
S-25
4.4.
(8R,9S,13S,14S,17S)-3-(3-Hydroxypropoxy)-13-methyl-7,8,9,11,12,1
3,14,15,16, 17-decahydro-6H-cyclopenta[a]phenanthren-17-ol (6f)
(8R,9S,13S,14S,17S)-3-(3-Hydroxypropoxy)-13-methyl-7,8,9,11,12,13,14,15,16,
17-decahydro-6H-cyclopenta[a]phenanthren-17-ol (6f) was prepared according to
reference.12 Starting from S7 (2.72 g, 10.0 mmol), The title compound 6f was
obtained as as a white solid (550 mg, 20% yield).
Melting point: 159–161 oC. 1H NMR (500 MHz, DMSO-d6) δ 7.14 (d, J = 8.6 Hz,
1H), 6.69–6.62 (m, 1H), 6.58 (s, 1H), 4.52–4.48 (m, 2H), 3.96 (t, J = 6.4 Hz, 2H),
3.55–3.49 (m, 3H), 2.75–2.74 (m, 2H), 2.25 (d, J = 10.7 Hz, 1H), 2.08 (t, J = 8.8 Hz,
13
1H), 1.91–1.77 (m, 5H), 1.60–1.55 (m, 1H), 1.40–1.06 (m, 8H), 0.66 (s, 3H). C
NMR (100 MHz, CDCl3) δ 156.40, 137.33, 132.06, 126.06, 114.07, 111.92, 80.02,
64.35, 57.37, 49.51, 43.49, 42.78, 36.56, 32.19, 29.88, 29.21, 26.85, 26.01, 22.75,
11.22. IR (thin film): 3231, 2927, 2867, 1641, 1572, 1498, 1474, 1254, 1054, 871,
778 cm–1. MS (EI, m/z, %): 330 (M+, 100.00); HRMS (EI): Calcd. For C21H30O3+:
330.2189; Found: 330.2197.
4.5. 5-(4-(3-Hydroxy-3-methylpentyl)phenoxy)pentan-1-ol (6g)
S-26
O O
K2CO3, acetone
+ Br OH
HO reflux, 12 h HO O
S8
OH
EtMgBr, Et2O
reflux, 12h
HO O
6g
4-(4-((5-Hydroxypentyl)oxy)phenyl)butan-2-one (S8) was prepared according to
reference.12 Starting from 4-(4-hydroxyphenyl)butan-2-one (1.64 g, 10.0 mmol), the
title compound S8 was obtained as a colorless oil (1.06 g, 40% yield).
1
H NMR (500 MHz, CDCl3) δ 7.07–7.05 (m, 2H), 6.80–6.77 (m, 2H), 3.92 (t, J =
6.4 Hz, 2H), 3.64 (t, J = 6.5 Hz, 2H), 2.82–2.79 (m, 2H), 2.72–2.69 (m, 2H),
13
2.12–2.11 (m, 3H), 1.81–1.75 (m, 2H), 1.65–1.58 (m, 2H), 1.55–1.48 (m, 2H). C
NMR (100 MHz, CDCl3) δ 208.48, 157.39, 132.85, 129.18, 114.48, 67.80, 62.62,
45.43, 32.37, 30.10, 29.04, 28.87, 22.34. IR (thin film): 3048, 3032, 2939, 2867, 1713,
1612, 1513, 1474, 1366, 1244, 1178, 1057, 1032, 821, 535 cm–1. MS (EI, m/z, %):
250 (M+, 17.06); 107 (100.00); HRMS (EI): Calcd. For C15H22O3+: 250.1563; Found:
250.1574.
5-(4-(3-Hydroxy-3-methylpentyl)phenoxy)pentan-1-ol (6g) was prepared
according to reference with modification.11 A 3-necked 50-mL round bottomed flask
(pre-dried by hot air gun under vacuo) fitted with a magnetic stirrer was evacuated/N2
filled for 3 times, and then S7 (500.0 mg, 2.0 mmol, 1.0 equiv) and Et2O (15 mL)
were added. After the dropwise addition of ethylmagnesium bromide (3 M in Et2O,
2.0 mL, 6.0 mmol, 3.0 equiv), the mixture was refluxed for 12 h. After cooling to
room temperature, water (5 mL) was added carefully and the mixture was extracted
with EtOAc (2 × 10 mL). The combined organic layers were dried over Na2SO4,
filtered, and concentrated under reduced pressure. The residue was purified by flash
column chromatography using dichloromethane/MeOH (15:1, v/v) to afford 6g as a
colorless oil (300.0 mg, 60% yield).
S-27
1
H NMR (400 MHz, CDCl3) δ 7.09 (d, J = 8.6 Hz, 2H), 6.81 (d, J = 8.6 Hz, 2H),
3.93 (t, J = 6.4 Hz, 2H), 3.65 (t, J = 6.4 Hz, 2H), 2.62–2.58 (m, 2H), 1.85 (s, 2H),
1.83–1.76 (m, 2H), 1.74–1.69 (m, 2H), 1.66–1.59 (m, 2H), 1.57–1.48 (m, 4H), 1.20 (s,
3H), 0.92 (t, J = 7.5 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 157.20, 134.68, 129.22,
114.54, 72.95, 67.92, 62.63, 43.48, 34.41, 32.45, 29.42, 29.13, 26.35, 22.42, 8.34. IR
(thin film): 3363, 3030, 2938, 2866, 1612, 1582, 1511, 1458, 1378, 1299, 1243, 1176,
1056, 1032, 938, 827, 531 cm–1. MS (EI, m/z, %): 280 (M+, 10.31); 147 (100.00);
HRMS (EI): Calcd. For C17H28O3+: 280.2033; Found: 280.2043.
4.6. 2-Methylpentane-2,4-diol (6h)
2-Methylpentane-2,4-diol (6h) was prepared according to reference.14 A 50 mL
round flask was charged sequentially with LiAlH4 (456 mg, 12 mmol, 1.2 equiv) and
THF (20 mL). 4-Hydroxy-4-methylpentan-2-one (1.16 g, 1.23 mL, 10 mmol, 1.0
equiv) was added dropwise. The mixture was stirred at room temperature for 3 h.
Upon completion, water (10 mL) was added carefully to quench the reaction. The
mixture was extracted with EtOAc (2 × 10 mL), dried over Na2SO4, filtered, and
concentrated under reduced pressure to afford 6h (624.8 mg, 53% yield) as colorless
oil.
1
H NMR (500 MHz, CDCl3) δ 4.17–4.12 (m, 1H), 3.84–3.73 (m, 2H), 1.62–1.56
(m, 1H), 1.45–1.40 (m, 1H), 1.25 (d, J = 4.5 Hz, 3H), 1.20 (d, J = 4.5 Hz, 3H),
1.15–1.12 (m, 3H). The characterization data are in agreement with previuos report.15
4.7. 3-Methylbutane-1,3-diol (6i)
S-28
3-Methylbutane-1,3-diol (6i) was prepared according to reference.14 A 50 mL
round flask was charged sequentially with LiAlH4 (570 mg, 15 mmol, 1.5 equiv) and
THF (20 mL). After cooling to 0 oC, 3-hydroxy-3-methylbutanoic acid (1.18 g, 1.03
mL, 10 mmol, 1 equiv) was added dropwise. The mixture was allowed to warm to
room temperature and stirred for 3 h. Upon completion, water (10 mL) was added
carefully to quench the reaction. The mixture was extracted with EtOAc (2 × 10 mL),
dried over Na2SO4, filtered, and concentrated under reduced pressure to afford 6i (402
mg, 39% yield) as colorless oil.
1
H NMR (500 MHz, CDCl3) δ 3.82 (t, J = 6.0 Hz, 2H), 3.48 (s, 2H), 1.68 (t, J =
5.9 Hz, 2H), 1.23 (s, 6H). The characterization data are in agreement with previuos
report.16
4.8.
(3R,5S,7R,8R,9S,10S,13R,14S,17R)-17-((R)-5-Hydroxypentan-2-yl)-1
0,13-dimethylhexadecahydro-1H-cyclopenta[a]phenanthrene-3,7-di
ol (6j)
S-29
(3R,5S,7R,8R,9S,10S,13R,14S,17R)-17-((R)-5-Hydroxypentan-2-yl)-10,13-dimeth
ylhexadecahydro-1H-cyclopenta[a]phenanthrene-3,7-diol (6j) was prepared
according to reference.9 Starting from S9 (1.96 g, 10.0 mmol), the title compound 6j
was obtained as as a white solid (1.23 g, 65% yield).
1
H NMR (400 MHz, CDCl3) δ 3.84–3.83 (m, 1H), 3.64–3.55 (m, 2H),
3.48–3.40 (m, 1H), 2.19 (dd, J = 24.6, 12.7 Hz, 1H), 1.98–1.93 (m, 2H), 1.90–1.78 (m,
5H), 1.72–1.57 (m, 4H), 1.50–1.33 (m, 8H), 1.31–1.19 (m, 4H), 1.16–1.03 (m, 4H),
1.00–0.96 (m, 1H), 0.93 (d, J = 6.4 Hz, 3H), 0.89 (s, 3H), 0.65 (s, 3H). The
characterization data are in agreement with previuos report.17
5. Deoxyfluorination of Alcohols 2 with SulfoxFluor
(1a)
General Procedures:
Into a 25-mL polytetrafluoroethylene (PTFE) tube were sequentially added
alcohol 2 (0.2 mmol), SulfoxFluor (1a) (83.4 mg, 0.24 mmol, 1.2 equiv), toluene (2.0
mL), and DBU (for primary alcohol, 36 μL, 0.24 mmol, 1.2 equiv; for secondary
alcohol, 48 μL, 0.32 mmol, 1.6 equiv), then the tube was sealed with a cap. The
mixture was stirred at room temperature for 10 minutes (for primary alcohol) or 30
minutes (for secondary alcohol). The system became cloudy once DBU was added,
corresponding to the formation of the protonated DBU salt of
4-chloro-N-tosylbenzenesulfonamide. The so-obtained reaction mixture was
concentrated under vacuum, and purified by chromatography on silica gel to afford
the desired alkyl fluoride. The yield of the alkene side product was determined by
GC-MS analysis of the crude reaction mixture.
For primary alcohols, the addition of external fluoride TBAF(tBuOH)4 can
increase about 10-20% yield of the desired alklyl fluorides. The general procedures
S-30
are given as follows: Into a 25-mL polytetrafluoroethylene (PTFE) tube were
sequentially added alcohol 2 (0.2 mmol), SulfoxFluor (83.4 mg, 0.24 mmol, 1.2
equiv), toluene (2.0 mL), TBAF(tBuOH)4 (110 mg, 1.0 equiv), and DBU (36 μL, 0.24
mmol, 1.2 equiv), then the tube was sealed with a cap. The mixture was stirred at room
temperature for 30 minutes. Thereafter, the reaction mixture was concentrated under
vacuum, and purified by chromatography on silica gel to afford the desired alkyl
fluoride.
2-(3-Fluorobutyl)naphthalene (3b)
Prepared from 4-(naphthalen-2-yl)butan-2-ol (2b) (40.0 mg, 0.2 mmol),

SulfoxFluor (1a) (83.4 mg, 0.24 mmol), and DBU (48 μL, 0.32 mmol)
(fluorination/elimination, 19:1); eluted with petroleum ether/EtOAc, 50:1 (v/v).
32.7 mg, 81% yield. Light yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.83–7.79 (m,
3H), 7.66 (s, 1H), 7.46 (pd, J = 6.8, 1.3 Hz, 2H), 7.36 (dd, J = 8.4, 1.4 Hz, 1H),
4.81–4.61 (m, 1H), 3.02–2.84 (m, 2H), 2.15–2.02 (m, 1H), 2.00–1.86 (m, 1H), 1.38 (dd,
13
J = 23.9, 6.2 Hz, 3H). C NMR (100 MHz, CDCl3) δ 138.96, 133.61, 132.02, 128.01,
127.61, 127.41, 127.23, 126.50, 125.97, 125.23, 90.03 (d, J = 165.0 Hz), 38.53 (d, J =
20.9 Hz), 31.50 (d, J = 4.8 Hz), 21.04 (d, J = 22.7 Hz). 19F NMR (376 MHz, CDCl3) δ
–174.3 (m, 1F). MS (EI, m/z, %): 202 (M+, 38.67), 141 (100.00), 142 (74.14); HRMS
(EI): Calcd. For C14H15F+: 202.1152; Found: 202.1162. The NMR data are in
agreement with the literature.7
1-(4-Fluoropentyl)naphthalene (3c)
S-31
Prepared from 5-(naphthalen-1-yl)pentan-2-ol (2c) (42.8 mg, 0.2 mmol),
33.7 mg, 78% yield. Colorless oil. 1H NMR (500 MHz, CDCl3) δ 8.06 (d, J = 8.3 Hz,
1H), 7.87 (d, J = 8.7 Hz, 1H), 7.74 (d, J = 8.2 Hz, 1H), 7.55–7.448 (m, 2H), 7.43–7.40
(m, 1H), 7.34 (d, J = 6.9 Hz, 1H), 4.80–4.64 (m, 1H), 3.13 (t, J = 7.5 Hz, 2H), 2.00–1.61
(m, 4H), 1.34 (dd, J = 23.9, 6.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 138.17, 133.89,
131.82, 128.78, 126.65, 125.96, 125.77, 125.50, 125.44, 123.73, 90.86 (d, J = 164.5
19
Hz), 36.84 (d, J = 20.7 Hz), 32.74, 26.21 (d, J = 4.6 Hz), 21.04 (d, J = 22.8 Hz). F
NMR (376 MHz, CDCl3) δ –172.50 (m, 1F). IR (thin film): 3046, 2977, 2936, 2868,
1596, 1509, 1458, 1386, 1133, 1087, 925, 799, 790, 778, 422 cm–1. MS (EI, m/z, %):
216 (M+, 26.46), 141 (100.00); HRMS (EI): Calcd. For C15H17F+: 216.1309; Found:
216.1306. The NMR data are in agreement with the literature.7
(R)-1-(Benzyloxy)-4-(4-fluoropentyl)benzene (3d)
Prepared from (R)-5-(4-(benzyloxy)- phenyl)pentan-2-ol (2d) (54.0 mg, 0.2 mmol),

39.1 mg, 72% yield; 39.1 mg, 72% yield [using DBU (1.6 equiv) and
TBAF(tBuOH)4 (1.0 equiv)]. White solid. Melting point: 36–38 oC. 1H NMR (400
MHz, CDCl3) δ 7.47 (d, J = 7.1 Hz, 2H), 7.42 (t, J = 7.7, 2H), 7.35 (t, J = 7.1 Hz, 1H),
7.13 (d, J = 8.5 Hz, 2H), 6.94 (d, J = 8.6 Hz, 2H), 5.07 (s, 2H), 4.79–4.72 (m, 0.5H),
4.67–4.60 (m, 0.5H), 2.62 (t, J= 7.3 Hz, 2H) 1.83–1.50 (m, 4H), 1.34 (dd, J = 23.9,
6.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 157.03, 137.22, 134.48, 114.72, 90.84 (d,
J = 164.5 Hz), 70.04, 36.37 (d, J = 20.7 Hz), 34.71, 27.03 (d, J = 4.7 Hz), 20.99 (d, J
19
= 22.8 Hz). F NMR (376 MHz, CDCl3) δ –172.95 (m, 1F). IR (thin film): 3060,
3027, 2978, 2939, 2859, 1611, 1582, 1514, 1456, 1387, 1254, 1131, 1044, 922, 830,
S-32
737, 696, 555, 493, 470 cm–1. MS (EI, m/z, %): 272 (M+, 14.68), 91 (100.00); HRMS
(EI): Calcd. For C18H21OF+: 272.1571; Found: 272.1581.
1-(3-Fluorobutyl)-4-methoxybenzene (3e)
Prepared from 4-(4-methoxyphenyl)butan-2-ol (2e) (36.0 mg, 0.2 mmol),

25.8 mg, 71% yield. Light yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.13 (d, J =
8.6 Hz, 2H), 6.85 (d, J = 8.6 Hz, 2H), 4.76–4.56 (m, 1H), 3.80 (s, 3H), 2.79–2.61 (m,
2H), 2.03–1.90 (m, 1H), 1.88–1.69 (m, 1H), 1.35 (dd, J = 23.9, 6.2 Hz, 3H). 13C NMR
(100 MHz, CDCl3) δ 157.86, 133.53, 129.33, 113.84, 90.04 (d, J = 164.7 Hz), 55.25,
38.91 (d, J = 20.8 Hz), 30.44 (d, J = 4.9 Hz), 21.01 (d, J = 22.7 Hz). 19F NMR (376
MHz, CDCl3) δ –174.27 (m, 1F). MS (EI, m/z, %): 182 (M+, 17.99), 121 (100.00);
HRMS (EI): Calcd. For C11H15OF+: 182.1101; Found: 182.1103. The NMR data are in
2-(5-Fluoropentyl)naphthalene (3f)
Prepared from 5-(naphthalen-2-yl)pentan-1-ol (2f) (42.8 mg, 0.2 mmol),

SulfoxFluor (1a) (83.4 mg, 0.24 mmol), and DBU (36 μL, 0.24 mmol) (no elimination
side product); eluted with petroleum ether/EtOAc, 50:1 (v/v).
35.8 mg, 83% yield. Light yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.84–7.79 (m,
3H), 7.64 (s, 1H), 7.46 (pd, J = 6.9, 1.4 Hz, 2H), 7.36 (dd, J = 8.4, 1.6 Hz, 1H), 4.47
(dt, J = 47.3, 6.1 Hz, 2H), 2.82 (t, J = 7.6 Hz, 2H), 1.83–1.70 (m, 4H), 1.55–1.47 (m,
2H). 13C NMR (100 MHz, CDCl3) δ 139.89, 133.61, 131.96, 127.82, 127.59, 127.39,
127.31, 126.34, 125.87, 125.07, 84.06 (d, J = 164.3 Hz), 35.94, 30.94, 30.30 (d, J =
S-33
19.5 Hz), 24.88 (d, J = 5.5 Hz). 19F NMR (376 MHz, CDCl3) δ –218.02 (tt, J = 47.4,
24.9 Hz). MS (EI, m/z, %): 216 (M+, 48.78), 141 (100.00); HRMS (EI): Calcd. For
C15H17F+: 216.1309; Found: 216.1308. The NMR data are in agreement with the
literature.7
4-(3-Fluoropropyl)-1,1'-biphenyl (3g)
Prepared from 3-([1,1'-biphenyl]-4-yl)propan-1-ol (2g) (42.4 mg, 0.2 mmol),

28.9 mg, 68% yield; 35.2 mg, 82% yield [using TBAF(tBuOH)4)]. Colorless oil.
1
H NMR (400 MHz, CDCl3) δ 7.62 (d, J = 8.2 Hz, 2H), 7.57 (d, J = 7.8 Hz, 2H), 7.47
(t, J = 7.6 Hz, 2H), 7.37 (t, J = 7.3 Hz, 1H), 7.31 (d, J = 7.9 Hz, 2H), 4.52 (dt, J =
13
47.2, 5.9 Hz, 2H), 2.85–2.81 (m, 2H), 2.15–2.01 (m, 2H). C NMR (100 MHz,
CDCl3) δ 141.00, 140.22, 139.06, 128.91, 128.74, 127.21, 127.10, 127.00, 83.12 (d, J
19
= 164.9 Hz), 32.01 (d, J = 19.8 Hz), 30.96 (d, J = 5.4 Hz). F NMR (376 MHz,
CDCl3) δ –220.50 (m, 1F). IR (thin film): 3056, 3028, 2963, 2861, 1487, 1449, 1410,
1389, 1076, 1063, 1029, 1008, 906, 845, 762, 731, 698 cm–1. MS (EI, m/z, %): 214
(M+, 36.83), 167 (100.00); HRMS (EI): Calcd. For C15H15F+: 214.1152; Found:
1-Fluorohexadecane (3h)
Prepared from hexadecan-1-ol (2h) (48.4 mg, 0.2 mmol), SulfoxFluor (1a) (83.4
mg, 0.24 mmol), and DBU (36 μL, 0.24 mmol) (no elimination side product); eluted
with petroleum ether/EtOAc, 50:1 (v/v).
41.8 mg, 84% yield. Colorless oil. 1H NMR (500 MHz, CDCl3) δ 4.48 (t, J = 6.2
Hz, 1H), 4.39 (t, J = 6.2 Hz, 1H), 1.69 (ddd, J = 24.8, 8.3, 6.5 Hz, 2H), 1.42–1.36 (m,
S-34
13
2H), 1.33–1.26 (m, 24H), 0.88 (t, J = 7.0 Hz, 3H). C NMR (100 MHz, CDCl3) δ
84.26 (d, J = 164.0 Hz), 31.96, 30.45 (d, J = 19.3 Hz), 29.73, 29.70, 29.68, 29.59,
29.56, 29.40, 29.29, 25.18 (d, J = 5.6 Hz), 22.73, 14.14. 19F NMR (376 MHz, CDCl3)
δ –218.02 (m, 1F). MS (EI, m/z, %): 244 (M+, 1.26), 57 (100.00); HRMS (EI): Calcd.
For C16H33F+: 244.2561; Found: 244.2568. The NMR data are in agreement with the
literature.18
2,3,4,6-Tetra-O-benzyl-D-glucopyranosyl fluoride (3i)
Prepared from 2,3,4,6-tetra-O-benzyl-D-glucopyranose (2i) (108.2 mg, 0.2 mmol),

(fluorination/elimination, >50:1); eluted with petroleum ether/EtOAc, 40:1 (v/v).
98.0 mg (β/α, 91.5:8.5), 90% yield. Light yellow oil. 1H NMR (400 MHz, CDCl3)
[8.5:91.5 mixture of α/β anomers]: δ 7.39–7.32 (m, 18H α and β), 7.21–7.19 (m, 2H α
and β), 5.61 (dd, J = 53.6, 2.0 Hz, 1H α), 5.31 (dd, J = 52.8, 6.7 Hz, 1H β), 5.01 (d, J
= 10.9 Hz, 1H α), 4.95 (d, J = 11.0 Hz, 1H β), 4.90 (d, J = 11.1 Hz, 1H α and β), 4.85
(t, J = 9.9 Hz, 2H α and β), 4.75 (d, J = 11.1 Hz, 1H α and β), 4.67 (d, J = 12.1 Hz, 1H
β), 4.63–4.55 (m, 2H α and β), 4.52 (d, J = 12.1 Hz, 1H α), 4.06–3.95 (m, 1H α)，
3.80–3.70 (m, 4H α and β), 3.68–3.58 (m, 2H β, 1H α). 13C NMR (100 MHz, CDCl3)
[β anomer]: δ 138.86, 137.97, 137.94, 137.79, 128.50, 128.47, 128.21, 128.11, 128.06,
127.99, 127.94, 127.89, 127.78, 109.93 (d, J = 216.0 Hz), 83.52 (d, J = 11.2 Hz),
81.55 (d, J = 21.7 Hz), 76.99, 75.48, 75.02, 74.92 (d, J = 4.8 Hz), 74.47 (d, J = 1.5
19
Hz), 73.65, 68.43. F NMR (376 MHz, CDCl3) [8.5:91.5 mixture of α/β anomers, α
denoted by *]: δ –137.98 (dd, J = 52.9, 11.6 Hz), –149.47 (dd, J = 53.0, 25.6 Hz)*.
MS (EI, m/z, %): 522 (M+ – HF, 100), 91 (100.00); HRMS (EI): Calcd. For
[C34H35FO5 – HF]+: 522.2401; Found: 522.2400. The NMR data are in agreement with
the literature.2
S-35
3α-Fluoro-5α-androstan-17-one (3j)
Prepared from 3β-hydroxy-5α-androstan-17-one (2j) (58.0 mg, 0.2 mmol),

(fluorination/elimination, 1.6:1); eluted with petroleum ether/EtOAc, 50:1 (v/v); the
elimination side products 3j’ (20.0 mg, 37% yield) was eluted first, followed by the
fluorination product 3j (34.0 mg, 58% yield).
White solid. 1H NMR (400 MHz, CDCl3) δ 4.80 (d, J = 48.6 Hz, 1H), 2.42 (dd, J
= 19.2, 8.6 Hz, 1H), 2.10–2.01 (m, 1H), 1.96–1.84 (m, 2H), 1.82–1.75 (m, 2H),
1.70–1.45 (m, 8H), 1.43–1.15 (m, 7H), 1.01 (qd, J = 12.8, 4.6 Hz, 1H), 0.85 (s, 3H),
13
0.80 (s, 3H). C NMR (100 MHz, CDCl3) δ 221.33 (s), 89.31 (d, J = 165.9 Hz),
54.22, 51.45, 47.79, 39.40, 35.88, 35.85, 35.03, 33.87 (d, J = 21.1 Hz), 32.38, 31.55,
30.77, 28.05, 27.04 (d, J = 21.9 Hz), 21.75, 20.06, 13.83, 11.16. 19F NMR (376 MHz,
CDCl3) δ –181.16 (m, 1F). MS (EI, m/z, %): 292 (M+, 100.00); HRMS (EI): Calcd.
For C19H29OF+: 292.2197; Found: 292.2207. The NMR data are in agreement with the
literature.2
5α-Androst-2-en-17-one and 5α-androst-3-en-17-one (3j’):
1
White solid. H NMR (400 MHz, CDCl3) [28.5:1 mixture of
5α-androst-2-en-17-one: 5α-androst-3-en-17-one; peaks overlap and are
indistinguishable]: δ 5.63–5.27 (m, 2H), 2.47–2.40 (m, 1H), 2.10–1.85 (m, 4H),
1.83–1.76 (m, 2H), 1.75–1.58 (m, 3H), 1.56–1.31 (m, 5H), 1.29–1.17 (m, 3H),
1.03–0.91 (m, 1H), 0.86–0.85 (m, 3H), 0.80–0.70 (m, 4H). The NMR data are in
2-(10-Fluorodecyl)-5,6-dimethoxy-3-methylcyclohexa-2,5-diene-1,4-dione (3k)
S-36
Prepared from idebenone (2k) (67.7 mg, 0.2 mmol), SulfoxFluor (1a) (83.4 mg,
0.24 mmol), and DBU (36 μL, 0.24 mmol) (no elimination side product); eluted with
petroleum ether/EtOAc, 50:1 (v/v).
48.9 mg, 72% yield; 56.6 mg, 82% yield [using TBAF(tBuOH)4)]. Yellow solid.
Melting point: 43–44 oC. 1H NMR (500 MHz, CDCl3) δ 4.46 (t, J = 6.2 Hz, 1H), 4.36
(t, J = 6.2 Hz, 1H), 3.97 (m, 6H), 2.44–2.41 (m, 2H), 1.99 (s, 3H), 1.71–1.61 (m, 2H),
13
1.39–1.23 (m, 14H). C NMR (100 MHz, CDCl3) δ 184.72, 184.16, 144.31, 144.30,
143.07, 138.68, 84.22 (d, J = 164.0 Hz), 61.15, 30.41 (d, J = 19.4 Hz), 29.81, 29.46,
29.39, 29.34, 29.21, 28.73, 26.40, 25.14 (d, J = 5.5 Hz), 11.91. 19F NMR (376 MHz,
1207, 1093, 747 cm–1. MS (EI, m/z, %): 340 (M+, 47.01), 197 (100.00); HRMS (EI):
Calcd. For C19H29O4F+: 340.2044; Found: 340.2054.
(E)-2-(5-Fluoropent-1-en-1-yl)naphthalene (3l)
Prepared from (E)-5-(naphthalen-2-yl)pent-4-en-1-ol (2l) (42.4 mg, 0.2 mmol),

35.6 mg, 76% yield; 37.0 mg, 86% yield [using TBAF(tBuOH)4)]. White solid.
Melting point: 38–39 oC. 1H NMR (400 MHz, CDCl3) δ 7.82–7.78 (m, 3H), 7.71 (s,
1H), 7.60 (dd, J = 8.5, 1.5 Hz, 1H), 7.49–7.42 (m, 2H), 6.62 (d, J = 15.8 Hz, 1H), 6.36
(dt, J = 15.7, 7.0 Hz, 1H), 4.55 (dt, J = 47.2, 6.0 Hz, 2H), 2.42 (td, J = 8.0, 1.2 Hz, 2H),
13
2.00–1.87 (m, 2H). C NMR (100 MHz, CDCl3) δ 134.95, 133.66, 132.74, 130.94 ,
129.64, 128.10, 127.85, 127.62, 126.18, 125.58, 125.54, 123.47, 83.36 (d, J = 164.8
19
Hz), 30.09 (d, J = 19.7 Hz), 28.70 (d, J = 5.5 Hz). F NMR (376 MHz, CDCl3) δ
S-37
–219.99 (m, 1F). IR (thin film): 3054, 2961, 2900, 2845, 1594, 1445, 1038, 1007, 972,
962, 904, 807, 740, 481, 471 cm–1. MS (EI, m/z, %): 214 (M+, 64.69), 167 (100.00);
HRMS (EI): Calcd. For C15H15F+: 214.1152; Found: 214.1154.
2-(5-Fluoropent-1-yn-1-yl)naphthalene (3m)
Prepared from 5-(naphthalen-2-yl)pent-4-yn-1-ol (2m) (42.0 mg, 0.2 mmol),

28.5 mg, 67% yield; 36.4 mg, 86% yield [using TBAF(tBuOH)4)]. Light yellow oil.
1
H NMR (400 MHz, CDCl3) δ 7.82–7.78 (m, 3H), 7.71 (s, 1H), 7.60 (dd, J = 8.5, 1.5
Hz, 1H), 7.49–7.42 (m, 2H), 6.62 (d, J = 15.8 Hz, 1H), 6.36 (dt, J = 15.7, 7.0 Hz, 1H),
4.55 (dt, J = 47.2, 6.0 Hz, 2H), 2.42 (td, J = 8.0, 1.2 Hz, 2H), 2.00–1.87 (m, 2H). 13C
NMR (100 MHz, CDCl3) δ 134.95, 133.66, 132.74, 130.94 , 129.64, 128.10, 127.85,
127.62, 126.18, 125.58, 125.54, 123.47, 83.36 (d, J = 164.8 Hz), 30.09 (d, J = 19.7
Hz), 28.70 (d, J = 5.5 Hz). 19F NMR (376 MHz, CDCl3) δ –221.95 (tt, J = 47.1, 25.8
Hz). IR (thin film): 3057, 2963, 2924, 2850, 2224, 1570, 1499, 1430, 1388, 1351,
1262, 1128, 1036, 894, 859, 818, 747, 474 cm–1. MS (EI, m/z, %): 212 (M+, 89.06),
165 (100.00); HRMS (EI): Calcd. For C15H13F+: 212.0996; Found: 212.0999.
1-((4-Bromophenyl)sulfonyl)-3-fluoropyrrolidine (3n)
F
N
Br S
O
O
Prepared from 1-((4-bromophenyl)sulfonyl)pyrrolidin-3-ol (2n) (61.1 mg, 0.2
mmol), SulfoxFluor (1a) (83.4 mg, 0.24 mmol), and DBU (48 μL, 0.32 mmol)
55.4 mg, 90% yield. White solid. Melting point: 115–117 oC. 1H NMR (500 MHz,
CDCl3) δ 7.70–7.65 (m, 4H), 5.20–5.08 (m, 1H), 3.57–3.53 (m, 2H), 3.49–3.48 (m,
S-38
1H), 3.26 (ddd, J = 10.9, 9.6, 6.5 Hz, 1H), 2.20–2.12 (m, 1H), 2.03–1.88 (m, 1H). 13C
NMR (100 MHz, CDCl3) δ 135.74, 132.41, 128.97, 127.93, 92.09 (d, J = 178.8 Hz),
54.42 (d, J = 23.7 Hz), 45.90, 32.54 (d, J = 21.7 Hz). 19F NMR (376 MHz, CDCl3) δ
–176.48 (m, 1F). IR (thin film): 3099, 2983, 2951, 2887, 1573, 1470, 1442, 1388,
1346, 1330, 1175, 1021, 1006, 744, 616, 578 cm–1. MS (EI, m/z, %): 307 (M+, 25.70),
88 (100.00); HRMS (EI): Calcd. For C10H11NO2FSBr+: 306.9672; Found: 306.9681.
(S)-4-(3-Fluoropyrrolidine-1-carbonyl)benzaldehyde (3o)
Prepared from (R)-4-(3-hydroxypyrrolidine-1-carbonyl)benzaldehyde (2o) (e.e. >

99.9%; 43.8 mg, 0.2 mmol), SulfoxFluor (1a) (83.4 mg, 0.24 mmol), and DBU (48 μL,
0.32 mmol) (fluorination/elimination, 24:1); eluted with petroleum ether/EtOAc, 3:1
(v/v).
39.6 mg, 90% yield. Light yellow oil. 1H NMR (400 MHz, CDCl3) [mixture of 2
rotamers] δ 10.03 (s, 1H), 7.91 (d, J = 7.8 Hz, 2H), 7.67 [7.62] (d, J = 8.1 Hz, 2H),
5.40–5.13 (m, 1H), 3.99–3.75 (m, 2H), 3.70–3.47 (m, 2H), 2.38–2.21 (m, 1H),
13
2.18–1.91 (m, 1H). C NMR (100 MHz, CDCl3) [mixture of 2 rotamers] δ 191.56,
168.59 [168.82], 141.88 [142.04], 137.26 [137.19], 129.78 [129.85], 127.83 [127.70],
91.45 [92.39] (d, J = 176.76 Hz), 53.00 [55.40] (d, J = 23.5 Hz), 46.90 [44.07], 33.09
19
[31.05] (d, J = 21.8 Hz). F NMR (376 MHz, CDCl3) [mixture of 2 rotamers] δ
–177.54 [–178.31] (m, 1F). MS (EI, m/z, %): 221 (M+, 45.95), 133 (100.00); HRMS
(EI): Calcd. For C12H12NO2F+: 221.0847; Found: 221.0856. The NMR data are in
HPLC Traces for Measuring Enantiomeric Excess: A racemic sample of
compound 3o was obtained through deoxyfluorination of racemic alcohol 2o with
SulfoxFluor (1a). The racemic and optically active 3o were analyzed with HPLC
(CHIRALPAK ID (0.46×25 cm, 5 um), hexane/IPA = 80/20 (v/v), λ = 214 nm, 0.70
S-39
mL/min) to determine the retention time and enantiomeric excesses. For (S)-3o, e.e. =
99.4%. [e.s.% = 99.4/99.9*100% = 99.5%]
(R)-Benzyl 3-fluoropyrrolidine-1-carboxylate (3p)
Prepared from (S)-benzyl 3-hydroxypyrrolidine-1-carboxylate (2p) (e.e. 99.8%;

45.0 mg, 0.2 mmol), SulfoxFluor (1a) (83.4 mg, 0.24 mmol), and DBU (48 μL, 0.32
mmol) (fluorination/elimination, 25:1); eluted with petroleum ether/EtOAc, 5:1 (v/v).
42.3 mg, 94% yield. Light yellow oil. NMR spectra are in agreement with the
literature.41H NMR (400 MHz, CDCl3) [mixture of 2 rotamers] δ 7.37–7.30 (m, 5H),
13
5.30–5.12 (m, 3H), 3.83–3.48 (m, 4H), 2.29–2.19 (m, 1H), 2.08–1.89 (m, 1H). C
NMR (100 MHz, CDCl3) [mixture of 2 rotamers] δ 154.84 [154.71], 136.76 [136.75],
128.49, 128.01, 127.94, 92.86 [92.03] (d, J = 176.0 Hz), 66.92, 52.90 [52.53] (d, J =
23.0 Hz), 43.98 [43.63], 32.48 [31.72] (d, J = 21.8 Hz). 19F NMR (376 MHz, CDCl3)
[mixture of 2 rotamers] δ –177.15 [–177.66] (m, 1F). MS (EI, m/z, %): 223 (M+,
S-40
16.31), 91 (100.00); HRMS (EI): Calcd. For C12H14NO2F+: 223.1003; Found:
compound 3p was obtained through deoxyfluorination of racemic alcohol 2p with
SulfoxFluor. The racemic and optically active 3p were analyzed with HPLC
(CHIRALPAK ID (0.46×25 cm, 5 um), hexane/IPA = 80/20 (v/v), λ = 214 nm, 0.70
mL/min) to determine the retention time and enantiomeric excesses. For (R)-3p, e.e. =
96.8%. [e.s.% = 96.8/99.8*100% = 97.0%]
(2S,4S)-1-tert-Butyl 2-methyl 4-fluoropyrrolidine-1,2-dicarboxylate (3q)
Prepared from N-Boc-trans-4-hydroxy-L-proline methyl ester (2q) (49.0 mg, 0.2

mmol), SulfoxFluor (1a) (83.4 mg, 0.24 mmol), and DBU (48 μL, 0.32 mmol)
S-41
38.0 mg, 77% yield. Colorless oil. 1H NMR (400 MHz, CDCl3) [mixture of 2
rotamers] δ 5.18 (d, J = 53.0 Hz, 1H, major and minor), 4.51 (d, J = 9.6 Hz, 1H,
minor), 4.40(d, J = 9.6 Hz, 1H, major), 3.90–3.53 (m, 2H, major and minor), 3.72 (s,
3H, major and minor), 3.70–3.51 (m, 1H), 2.50–2.22 (m, 2H, major and minor), 1.46
13
(s, 9H, minor), 1.41 (s, 9H, major). C NMR (100 MHz, CDCl3) [mixture of two
rotamers, minor rotamer denoted by *] δ 172.30, 171.91*, 154.04*, 153.67, 92.23* (d,
J = 176.0 Hz), 91.16 (d, J = 176.0Hz), 80.44*, 80.40, 57.65, 57.26*, 53.20* (d, J =
24.4 Hz), 52.87 (d, J = 24.4 Hz), 52.38*, 52.24, 37.47 (d, J = 22.1 Hz), 36.61* (d, J =
19
21.8 Hz), 28.39*, 28.27. F NMR (376 MHz, CDCl3) δ –173.14 (m, 1F). MS (EI,
m/z, %): 247 (M+, 0.17), 57 (100.00); HRMS (EI): Calcd. For C11H18NO4F+:
247.1214; Found: 247.1217. The NMR data are in agreement with the literature.2
4-(3-Fluoropropyl)pyridine (3r)
Prepared from 3-(pyridin-4-yl)propan-1-ol (2r) (27.4 mg, 0.2 mmol), SulfoxFluor

(1a) (83.4 mg, 0.24 mmol), and DBU (36 μL, 0.24 mmol) (no elimination side product);
eluted with petroleum ether/EtOAc, 4:1 (v/v).
1
H NMR (500 MHz, CDCl3) δ 8.54 (s, 2H), 7.14 (d, J = 2.4 Hz, 2H), 4.45 (dt, J =
47.1, 5.8 Hz, 2H), 2.76–2.73 (m, 2H), 2.01 (dddd, J = 15.2, 13.3, 10.0, 5.9 Hz, 2H).
13
C NMR (100 MHz, CDCl3) δ 150.13, 149.76, 124.06, 82.69 (d, J = 165.8 Hz), 30.39
(d, J= 75 Hz), 30.81. 19F NMR (376 MHz, CDCl3) δ –220.89 (m, 1F). IR (thin film):
3398, 3071, 3029, 2965, 1064, 1559, 1417, 1390, 1220, 1027, 1001, 907, 799 cm–1.
MS (EI, m/z, %): 139 (M+, 64.88), 93 (100.00); HRMS (EI): Calcd. For C8H10NF+:
139.0792; Found: 139.0800.
(S)-Ethyl 2-fluoro-4-phenylbutanoate (3s)
S-42
Prepared from (R)-ethyl 2-hydroxy-4-phenylbutanoate (2s) (e.e. > 99.9%; 41.6 mg,
0.2 mmol), SulfoxFluor (1a) (83.4 mg, 0.24 mmol), and DBU (48 μL, 0.32 mmol)
27.3 mg, 65% yield. Colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.33–7.29 (m,
2H), 7.24–7.20 (m, 3H), 4.97–4.81 (m, 1H), 4.22 (q, J = 7.1 Hz, 2H), 2.84–2.75 (m,
13
2H), 2.27–2.15 (m, 2H), 1.29 (t, J = 7.1 Hz, 3H). C NMR (100 MHz, CDCl3) δ
169.88 (d, J = 23.6 Hz), 140.21, 128.58, 128.55, 126.33, 88.05 (d, J = 184.4 Hz),
19
61.52, 34.09 (d, J = 21.0 Hz), 30.52 (d, J = 3.4 Hz), 14.17. F NMR (376 MHz,
1739, 1497, 1456, 1374, 1274, 1212, 1092, 1051, 1029, 2748, 701 cm–1. MS (EI,
m/z, %): 210 (M+, 45.06), 91 (100.00); HRMS (EI): Calcd. For C12H15O2F+: 210.1051;
Found: 210.1050.
compound 3s was obtained through deoxyfluorination of racemic alcohol 2s with
SulfoxFluor. The racemic and optically active 3s were analyzed with HPLC (Amy
lose-2, ID (0.46×25 cm, 5 um), hexane/IPA = 80/20 (v/v), λ = 214 nm, 0.70 mL/min)
to determine the retention time and enantiomeric excesses. For (S)-3s, e.e. = 99.2%.
[e.s.% = 99.2/99.9*100% = 99.3%]
S-43
1-(2-Fluoroethyl)naphthalene (3t)
Prepared from 2-(naphthalen-1-yl)ethan-1-ol (2t) (34.8 mg, 0.2 mmol),

1
H NMR (400 MHz, CDCl3) δ 8.04 (d, J= 8.3 Hz, 1H), 7.89 (d, J = 8.1 Hz, 1H), 7.79
(d, J = 7.8 Hz, 1H), 7.58–7.50 (m, 2H), 7.47–7.40 (m, 2H), 4.79 (dt, J = 47.0, 6.9 Hz,
2H), 3.53 (dt, J = 20.3, 6.9 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 133.87, 132.78 (d,
J = 7.5 Hz), 131.99, 128.89, 127.56, 127.17, 126.18, 125.66, 125.53, 83.51 (d, J =
169.6 Hz), 33.83 (d, J = 20.8 Hz). 19F NMR (376 MHz, CDCl3) δ –213.4 (m, 1F). MS
(EI, m/z, %): 174 (M+, 36.47), 141 (100.00); HRMS (EI): Calcd. For C11H11F+:
174.0839; Found: 174.0848. The NMR data are in agreement with the literature.19
4-(2-Fluoroethyl)-1,2-dimethoxybenzene (3u)
Prepared from 2-(3,4-dimethoxyphenyl)ethanol (2u) (36.4 mg, 0.2 mmol),

1
H NMR (400 MHz, CDCl3) δ 6.83–6.76 (m, 3H), 4.61 (d, J = 47.2 Hz, 2H), 3.88 (s,
13
3H), 3.86 (s, 3H), 2.96 (dt, J = 23.3, 6.6 Hz, 2H). C NMR (100 MHz, CDCl3) δ
148.94, 147.83, 129.67 (d, J = 6.3 Hz), 120.91, 112.22, 111.31, 84.31 (d, J = 168.9
S-44
Hz), 55.91, 55.84, 36.52 (d, J = 20.3 Hz). 19F NMR (376 MHz, CDCl3) δ –215.48 (m,
1F). MS (EI, m/z, %): 184 (M+, 49.88), 151 (100.00); HRMS (EI): Calcd. For
C10H13O2F+: 184.0894; Found: 184.0901. The NMR data are in agreement with the
literature.2
5-(2-Fluoroethyl)-4-methylthiazole (3v)
Prepared from 2-(4-methylthiazol-5-yl)ethanol (2v) (28.6 mg, 0.2 mmol),

1
H NMR (400 MHz, CDCl3) δ 8.60 (s, 1H), 4.57 (dt, J = 46.8, 6.2 Hz, 2H), 3.16 (dt, J
13
= 23.5, 6.2 Hz, 2H), 2.41 (s, 3H). C NMR (100 MHz, CDCl3) δ 150.08, 150.05,
125.82, 83.08 (d, J = 170.8 Hz), 27.62 (d, J = 22.0 Hz), 14.89. 19F NMR (376 MHz,
CDCl3) δ –215.44 (m, 1F). MS (EI, m/z, %): 145 (M+, 49.85), 112 (100.00); HRMS
(EI): Calcd. For C6H8NFS+: 145.0356; Found: 145.0358. The NMR data are in
3-(2-Fluoroethyl)benzofuran (3w)
Prepared from 2-(benzofuran-3-yl)ethanol (2w) (32.4 mg, 0.2 mmol), SulfoxFluor

(1a) (83.4 mg, 0.24 mmol), and DBU (36 μL, 0.24 mmol) (no elimination side product);
eluted with petroleum ether/EtOAc, 6:1 (v/v).
1
H NMR (500 MHz,CDCl3) δ 7.58–7.49 (m, 3H), 7.33–7.27 (m, 2H), 4.77 (t, J = 6.3
Hz, 1H), 4.68 (t, J = 6.3 Hz, 1H), 3.10 (dtd, J = 23.9, 6.3, 0.9 Hz, 2H). 13C NMR (100
MHz, CDCl3) δ 155.28, 142.21, 142.20, 127.88, 124.39, 122.51, 119.43, 111.55,
19
82.76 (d, J = 169.0 Hz), 25.08 (d, J = 21.9 Hz). F NMR (376 MHz, CDCl3) δ
S-45
–215.02 (m, 1F). IR (thin film): 3120, 3060, 2964, 2917, 2850, 1810, 1749, 1582,
1453, 1272, 1185, 1097, 1008, 858, 745, 419 cm–1. MS (EI, m/z, %): 164 (M+, 47.28),
131 (100.00); HRMS (EI): Calcd. For C10H9OF+: 164.0632; Found: 164.0641.
1-Fluoro-4-(2-fluoroethyl)benzene (3x)
Prepared from 2-(4-fluorophenyl)ethanol (2x) (56.0 mg, 0.4 mmol), SulfoxFluor

(166.8 mg, 0.48 mmol), toluene (4 mL), and DBU (72 μL, 0.48 mmol). The reaction
19
mixture was determined by F NMR spectrum analysis to give a ratio of 11:1
fluorination/elimination selectivity [when TBAF(tBuOH)4) (1.0 equiv) was used as an
additive, fluorination/elimination, > 70:1]; eluted with petroleum ether/EtOAc, 50:1
(v/v).
1
H NMR (400 MHz, CDCl3) δ 7.22–7.18 (m, 2H), 7.03–6.99 (m, 2H), 4.89–4.54 (m,
2H), 2.99 (dt, J = 23.9, 6.4 Hz, 2H). 13C NMR (125 MHz, CDCl3) δ 162.92, 160.97,
130.54 (d, J = 7.9 Hz), 115.49 (d, J = 21.3 Hz), 84.13 (d, J = 169.0 Hz), 36.26 (d, J =
20.5 Hz). 19F NMR (376 MHz, CDCl3) δ –117.03 (m, 1F), –216.37 (m, 1F). IR (thin
film): 3041, 2961, 2925, 2855 1569, 1511, 1224, 1160, 1063, 1015, 824, 555. 504
cm-1. HRMS (EI): Calcd. For C8H8F2+: 142.0589; Found: 142.0590.
6. Deoxyfluorination of Multiple Alcohols 4 with
SulfoxFluor (1a)
General Procedures:
S-46
multiple alcohol 6 (0.2 mmol), SulfoxFluor (1a) (83.4 mg, 0.24 mmol, 1.2 equiv),
toluene (2.0 mL), and DBU (36 μL, 0.24 mmol, 1.2 equiv; or 48 μL, 0.32 mmol, 1.6
equiv), then the tube was sealed with a cap. The mixture was stirred at room
temperature for 30 minutes. The system became cloudy once DBU was added,
corresponding to the formation of the protonated DBU salt of
4-chloro-N-tosylbenzenesulfonamide. The so-obtained reaction mixture was
concentrated under vacuum, and purified by chromatography on silica gel to afford
the desired alkyl fluoride 7.
For the fluorination of primary alcohol functional group, the addition of external
fluoride TBAF(tBuOH)4 can increase the desired alklyl fluorides to some extent. The
general procedures are given as follows: Into a 25-mL polytetrafluoroethylene (PTFE)
tube were sequentially added alcohol 2 (0.2 mmol), SulfoxFluor (83.4 mg, 0.24 mmol,
1.2 equiv), toluene (2.0 mL), TBAF(tBuOH)4 (110 mg, 1.0 equiv), and DBU (36 μL,
0.24 mmol, 1.2 equiv; or 48 μL, 0.32 mmol, 1.6 equiv), then the tube was sealed with
a cap. The mixture was stirred at room temperature for 30 minutes. Thereafter, the
reaction mixture was concentrated under vacuum, and purified by chromatography on
silica gel to afford the desired alkyl fluoride.
4-(4-(3-Fluoropropoxy)phenyl)butan-2-ol (7a)
Prepared from 4-(4-(3- hydroxypropoxy)phenyl)butan-2-ol (6a) (44.8 mg, 0.2

mmol), SulfoxFluor (1a) (83.4 mg, 0.24 mmol), and DBU (36 μL, 0.24 mmol) (10
minutes); eluted with petroleum ether/EtOAc 4:1 (v/v).
1
H NMR (400 MHz, CDCl3) δ 7.11 (d, J = 8.5 Hz, 2H), 6.83 (d, J = 8.6 Hz, 2H), 4.64
(dt, J = 47.1, 5.8 Hz, 2H), 4.07 (t, J = 6.1 Hz, 2H), 3.85 – 3.78 (m, 1H), 2.73 – 2.58
(m, 2H), 2.16 (dp, J = 25.9, 6.0 Hz, 2H), 1.80–1.67 (m, 2H), 1.45 (s, 1H), 1.22 (d, J =
S-47
6.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 156.96, 134.32, 129.31, 114.47, 80.82 (d,
J = 164.3 Hz), 67.51, 63.52 (d, J = 5.3 Hz), 41.06, 31.22, 30.48 (d, J = 20.0 Hz),
19
23.63. F NMR (376 MHz, CDCl3) δ –222.68 (m, 1F). IR (thin film): 3382, 3031,
2967, 2928, 1729, 1612, 1583, 1510, 1474, 1298, 1243, 1177, 1129, 1055, 986, 953,
827 cm–1. MS (EI, m/z, %): 226 (M+, 46.42), 107 (100.00); HRMS (EI): Calcd. For
C13H19O2F+: 226.1364; Found: 226.1371. The NMR data are in agreement with the
literature.7
(3R,5R,8R,9S,10S,13R,14S,17R)-17-((R)-5-Fluoropentan-2-yl)-10,13-dimethylhex
adecahydro-1H-cyclopenta[a]phenanthren-3-ol (7b)
Prepared from 3α-hydroxy-5β-cholan-24-ol (6b) (72.4 mg, 0.2 mmol), SulfoxFluor

(1a) (83.4 mg, 0.24 mmol), and DBU (48 μL, 0.32 mmol); eluted with petroleum
ether/EtOAc 25:1 (v/v).
Melting point: 131–135 oC. 1H NMR (500 MHz, CDCl3) δ 4.40 (dt, J = 47.4, 6.2 Hz,
2H), 3.65–3.58 (m, 1H), 1.96 (dt, J = 12.3, 3.0 Hz, 1H), 1.87–1.76 (m, 4H), 1.74–1.60
(m, 3H), 1.59–1.45 (m, 4H), 1.44–1.36 (m, 6H), 1.36–1.30 (m, 1H), 1.29–1.21 (m,
3H), 1.11–0.96 (m, 7H), 0.93–0.91 (m, 6H), 0.64 (s, 3H). 13C NMR (100 MHz, CDCl3)
δ 84.72 (d, J = 164.3 Hz), 71.86, 56.51, 56.10, 42.71, 42.10, 40.45, 40.20, 36.44,
35.85, 35.42, 35.36, 34.58, 31.16 (d, J = 5.2 Hz), 30.54, 28.27, 27.21, 27.08 (d, J =
19
19.3 Hz), 26.43, 24.21, 23.38, 20.83, 18.53, 12.05. F NMR (376 MHz, CDCl3) δ
–217.17 (m, 1F). IR (thin film): 3308, 2931, 2863, 1467, 1449, 1377, 1365, 1308,
1170, 1070, 1040, 1012, 897, 721, 615 cm–1. MS (EI, m/z, %): 364 (M+, 15.95), 215
(100.00); HRMS (EI): Calcd. For C24H41OF+: 364.3136; Found: 364.3138.
3-(Fluoromethyl)heptan-4-ol (7c)
S-48
Prepared from 2-ethylhexane-1,3-diol (6c) (73.0 mg, 0.5 mmol; mixture of 2
diastereoisomers, d.r. 1:1), SulfoxFluor (1a) (208.5 mg, 0.6 mmol), and DBU (120 μL,
0.6 mmol) in toluene (5.0 mL); eluted with pentane/Et2O 25:1 (v/v).
46.2 mg, 63% yield. Colorless oil. 1H NMR (500 MHz, CDCl3) [mixture of 2
diastereoisomers, d.r. 1:1] δ 4.68–4.46 (m, 2H), 3.81–3.68 (m, 1H), 1.72–1.58 (m,
2H), 1.57–1.30 (m, 6H), 0.99–0.94 (m, 6H). 13C NMR (100 MHz, CDCl3) [mixture of
2 diastereoisomers, d.r. 1:1] δ 84.51 [83.80] (d, J = 166.65 Hz), 71.88 [71.84] (d, J =
11.11 Hz), 46.26 [46.18] (d, J = 16.16 Hz), 37.26 [36.22], 20.36 [18.02] (d, J = 5.8
Hz), 19.47 [19.19], 14.06, 12.20 [11.72]. 19F NMR (376 MHz, CDCl3) [mixture of 2
diastereoisomers, d.r. 1:1] δ –225.88 [–227.61] (m, 1F). IR (thin film): 3400, 2962,
2935, 2876, 1465, 1382, 1145, 1114, 1014, 963, 849 cm–1. MS (EI, m/z, %): 148 (M+,
0.09), 56 (100.00); HRMS (EI): Calcd. For [C8H17OF–H]+: 147.1180; Found:
147.1181.
8-Fluoro-3-phenethyl-1-phenyloctan-3-ol (7d)
Prepared from 6-phenethyl- 8-phenyloctane-1,6-diol (6d) (65.2 mg, 0.2 mmol),

SulfoxFluor (1a) (83.4 mg, 0.24 mmol), and DBU (36 μL, 0.24 mmol); eluted with
petroleum ether/EtOAc 10:1 (v/v).
53.0 mg, 80% yield. Colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.34–7.31 (m,
4H), 7.26–7.20 (m, 6H), 4.48 (dt, J = 47.3, 6.1 Hz, 2H), 2.72–2.68 (m, 4H), 1.88–1.83
13
(m, 4H), 1.81–1.69 (m, 2H), 1.64–1.61 (m, 2H), 1.51–1.42 (m, 5H). C NMR (100
MHz, CDCl3) δ 142.41, 128.53, 128.37, 125.92, 84.12 (d, J = 164.3 Hz), 74.28, 41.29,
39.12, 30.43 (d, J = 19.5 Hz), 30.08, 25.91 (d, J = 5.2 Hz), 23.31. 19F NMR (376 MHz,
S-49
2863, 1602, 1496, 1455, 1389, 1031, 933, 747, 699, 518 m–1. MS (EI, m/z, %): 310
(M+ – H2O, 9.96), 91 (100.00); HRMS (EI): Calcd. For [C22H29OF – H2O]+: 310.2091;
Found: 310.2105.
4-(4-(3-Fluoropropoxy)phenyl)cyclohexanol (7e)
Prepared from 4-(4-(3-hydroxypropoxy)phenyl)cyclohexanol (6e) (50.0 mg, 0.2

mmol), SulfoxFluor (1a) (83.4 mg, 0.24 mmol), and DBU (48 μL, 0.32 mmol); eluted
with petroleum ether/EtOAc 5:1 (v/v).
20.0 mg, 40% yield. White solid. Melting point: 94–96 oC. 1H NMR (400 MHz,
CDCl3) δ 7.11 (d, J = 8.6 Hz, 2H), 6.84 (d, J = 8.7 Hz, 2H), 4.64 (dt, J = 47.1, 5.8 Hz,
2H), 4.07 (t, J = 6.1 Hz, 2H), 3.70–3.65 (m, 1H), 2.48–2.41 (m, 1H), 2.22–2.07 (m,
4H), 1.92–1.89 (m, 2H), 1.57 (s, 1H), 1.55–1.36 (m, 4H). 13C NMR (100 MHz, CDCl3)
δ 157.04, 138.94, 127.65, 114.35, 80.81 (d, J = 164.3 Hz), 70.67, 63.46 (d, J = 5.3 Hz),
42.52, 35.96, 32.65, 30.46 (d, J = 20.0 Hz). 19F NMR (376 MHz, CDCl3) δ –222.73
(m, 1F). IR (thin film): 3421, 2981, 2954, 2925, 2854, 1614, 1516, 1472, 1275, 1243,
1183, 1055, 1014, 964, 842, 814, 546 cm–1. MS (EI, m/z, %): 252 (M+, 0.34), 97
(100.00); HRMS (EI): Calcd. For C15H21O2F+: 252.1520; Found: 252.1532.
(8R,9S,13S,14S,17S)-3-(3-Fluoropropoxy)-13-methyl-7,8,9,11,12,13,14,15,16,17-
decahydro-6H-cyclopenta[a]phenanthren-17-ol (7f)
OH
H H
F O
Prepared from (8R,9S,13S,14S,17S)-3-(3-
hydroxypropoxy)-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]
phenanthren-17-ol (6f) (66.0 mg, 0.2 mmol), SulfoxFluor (83.4 mg, 0.24 mmol), and
DBU (48 μL, 0.32 mmol); eluted with petroleum ether/EtOAc 10:1 (v/v).
S-50
Melting point: 94–97 oC. 1H NMR (500 MHz, CDCl3) δ 7.21 (d, J = 8.6 Hz, 1H), 6.72
(dd, J = 8.6, 2.7 Hz, 1H), 6.64 (d, J = 2.6 Hz, 1H), 4.64 (dt, J = 47.1, 5.8 Hz, 2H),
4.07 (t, J = 6.1 Hz, 2H), 3.73 (t, J = 8.5 Hz, 1H), 2.87–2.84 (m, 2H), 2.34–2.29 (m,
1H), 2.22–2.09 (m, 4H), 1.95 (dt, J = 12.6, 3.3 Hz, 1H), 1.91–1.86 (m, 1H), 1.74–1.67
(m, 1H), 1.58 (s, 1H), 1.54–1.26 (m, 6H), 1.23–1.17 (m, 1H), 0.78 (s, 3H). 13C NMR
(100 MHz, CDCl3) δ 156.63, 138.06, 132.89, 126.38, 114.52, 112.02, 81.91, 80.87 (d,
J = 164.3 Hz), 63.44 (d, J = 5.4 Hz), 50.05, 43.97, 43.28, 38.86, 36.73, 30.60, 30.41,
29.81, 27.26, 26.34, 23.15, 11.08. 19F NMR (376 MHz, CDCl3) δ –222.66 (m, 1F). IR
(thin film): 3494, 2914, 2863, 1609, 1573, 1498, 1473, 1379, 1253, 1055, 1010, 957,
874, 810cm–1. MS (EI, m/z, %): 332 (M+, 100.00); HRMS (EI): Calcd. For
C21H29O2F+: 332.2146; Found: 332.2156.
1-(4-((5-Fluoropentyl)oxy)phenyl)-3-methylpentan-3-ol (7g)
OH
F O
Prepared from 5-(4-(3-hydroxy-3-methylpentyl)- phenoxy)-pentan-1-ol (6g) (56.0

mg, 0.2 mmol), SulfoxFluor (1a) (83.4 mg, 0.24 mmol), and DBU (36 μL, 0.24
mmol); eluted with petroleum ether/EtOAc 20:1 (v/v).
36.5 mg, 65% yield. Colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.11 (d, J = 8.6
Hz, 2H), 6.82 (d, J = 8.6 Hz, 2H), 4.47 (dt, J = 47.3, 6.1 Hz, 2H), 3.95 (t, J = 6.4 Hz,
2H), 2.63–2.59 (m, 2H), 1.86–1.71 (m, 6H), 1.63–1.50 (m, 6H), 1.22 (s, 3H), 0.93 (t,
13
J = 7.5 Hz, 3H). C NMR (100 MHz, CDCl3) δ 157.17, 134.65, 129.17, 114.49,
83.99 (d, J = 164.5 Hz), 72.85, 67.68, 43.47, 34.42, 30.16 (d, J = 19.6 Hz), 29.39,
28.95, 26.35, 21.94 (d, J = 5.5 Hz), 8.26. 19F NMR (376 MHz, CDCl3) δ –218.87 (m,
1F). IR (thin film): 3420, 3030, 2964, 2939, 2869, 1612, 1151, 1459, 1389, 1299,
1243, 1176, 1053, 1030, 938, 829, 530 cm–1. MS (EI, m/z, %): 282 (M+, 0.16), 97
(100.00); HRMS (EI): Calcd. For C17H27O2F+: 282.1990; Found: 282.1988.
S-51
4-Fluoro-2-methylpentan-2-ol (7h)
Performed with 2-methylpentane-2,4-diol (6h) (23.6 mg, 0.2 mmol), SulfoxFluor

(1a) (83.4 mg, 1.2 equiv), and DBU (48 μL, 0.32 mmol). Upon completion,
19
of 5h was determined to be 51% by F NMR analysis. When TBAF(tBuOH)4 (110
mg, 0.2 mmol) was used as an additive, The yield of 7h was determined to be 43% by
19
F NMR analysis.
19 o
F NMR (376 MHz, 23 C, in toluene) δ –170.06 (7h), –123.90
(1-fluoronaphthalene).
4-Fluoro-2-methylbutan-2-ol (7i)
Performed with 3-methylbutane-1,3-diol (6i) (20.8 mg, 0.2 mmol), SulfoxFluor (1a)
(83.4 mg, 0.24 mmol), and DBU (48 μL, 0.32 mmol). Upon completion,
of 7i was determined to be 56% by 19F NMR analysis. When TBAF(tBuOH)4 (110 mg,
0.2 mmol) was used as an additive, The yield of 7i was determined to be 70% by 19F
NMR analysis.
19 o
F NMR (376 MHz, 23 C, in toluene) δ –218.72 (7i), –123.90
(1-fluoronaphthalene).
(3R,5S,7R,8R,9S,10S,13R,14S,17R)-17-((R)-5-Fluoropentan-2-yl)-10,13-dimethyl
hexadecahydro-1H-cyclopenta[a]phenanthrene-3,7-diol (7j)
S-52
F
H
H H
HO OH
H
Prepared from alcohol 6j (75.6 mg, 0.2 mmol), SulfoxFluor (1a) (104.3 mg, 0.3
mmol), and DBU (60 μL, 0.4 mmol) at 80 oC for 30 minutes (DBU was added at 80
o
C); eluted with petroleum ether/EtOAc 2:1 (v/v).
30.3 mg, 41% yield. Colorless oil. 1H NMR (400 MHz, CDCl3) δ 4.46 (t, J = 6.2
Hz, 1H), 4.34 (t, J = 6.1 Hz, 1H), 3.84–3.83 (m, 1H), 3.49–3.41 (m, 1H), 2.20 (dd, J =
24.9, 12.7 Hz, 1H), 1.99–1.93 (m, 2H), 1.92–1.78 (m, 5H), 1.75–1.55 (m, 5H),
1.51–1.44 (m, 4H), 1.41–1.34 (m, 3H), 1.32–1.22 (m, 3H), 1.20–1.05 (m, 4H),
1.01–0.92 (m, 4H), 0.90 (s, 3H), 0.66 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 84.67 (d,
J = 164.3 Hz), 71.98, 68.52, 55.93, 50.47, 42.66, 41.50, 39.83, 39.68, 39.42, 35.42,
35.35, 35.05, 34.62, 32.86, 31.17 (d, J = 5.2 Hz), 30.66, 28.23, 27.04 (d, J = 19.3 Hz),
23.69, 22.80, 20.60, 18.54, 11.78. 19F NMR (376 MHz, CDCl3) δ –217.84 (m, 1F). IR
(thin film): 3378, 2931, 2866, 1712, 1469, 1450, 1377, 1339, 1079, 1050, 999, 903,
606 cm–1. MS (EI, m/z, %): 380 (M+, 4.55), 95 (100.00); HRMS (ESI): Calcd. For
C24H45O2NF+, 398.3429; Found: 398.3430.
7. Gram-Scale Deoxyfluorination of Alcohol 2n with
SulfoxFluor (1a)
alcohol 2n (1.525 g, 5.0 mmol), SulfoxFluor (1a) (2.085 g, 6.0 mmol), toluene (50.0
S-53
mL), and DBU (1.2 mL, 8.0 mmol), then the tube was sealed with a cap. The mixture
was stirred at room temperature for 30 minutes. After filtration, the filtrate was
concentrated under vacuum, and purified by chromatography on silica gel [petroleum
ether/EtOAc, 10:1 (v/v)] to afford the desired alkyl fluoride 3n as white solids (1.345
g, 88% yield).
8. Mass Balance Analysis of the Deoxyfluorination of
Primary Alcohols
8.1 Deoxyfluorination of Alcohol 2t
The reaction was performed on 0.2-mmol scale in a polytetrafluoroethylene
(PTFE) tube following the general proceduces for deoxyfluorination of primary
alcohols. Upon the completion of the reaction, CH2Cl2 (5.0 mL) was added to dissolve
19
the solids. The yield of alkyl fluoride 3t was determined to be 79% by F NMR
analysis using 1-fluoronaphthalene as internal standard. GC-MS analysis showed that
no elimination side product 3t’ was generated. According to the mass balance of
alcohol 2t, the residue 21% of the alkyl from 2t was attributed to the formation of the
N-alkylation byproduct 3t’’. LC-MS analysis confirmed the existence of the
ammonium salt 3t’’ [ESI (cation+): 307.0; (anion–): 343.8] (Figures S3 and S4).
S-54
Figure S3. The mass spectrum of the cation of 3t’’
Figure S4. The mass spectrum of the anion of 3t’’
8.2 Deoxyfluorination of Alcohol 2v
S-55
alcohols. Upon the completion of the reaction, CH2Cl2 (5.0 mL) was added to dissolve
19
the solids. The yield of alkyl fluoride 3t was determined to be 65% by F NMR
analysis using 1-fluoronaphthalene as internal standard. GC-MS analysis showed that
no elimination side product 3v’ was generated. According to the mass balance of
alcohol 2v, the residue 35% of the alkyl from 2v was attributed to the formation of the
N-alkylation byproduct 3v’’. LC-MS analysis confirmed the existence of the
ammonium salt 3v’’ [ESI (cation+): 278.0; (anion–): 343.7] (Figures S5 and S6).
S-56
Figure S5. The mass spectrum of the cation of 3v’’
Figure S6. The mass spectrum of the anion of 3v’’
9. Recovery of Deoxyfluorination Byproduct
S-57
alcohols. Upon the completion of the reaction, the solids were collected by filtration,
washed with toluene (20 mL), and dried under vacuum at room temperature for 2
hours to give the deoxyfluorination byproduct (1.81 g). Meanwhile, the filtrate was
concentrated in vacuo and purified by chromatography on silica gel [petroleum
ether/EtOAc 50:1 (v/v)] to give 3t as a light yellow oil (461.5 mg, 77% yield).
(*)1H NMR analysis showed that the N-alkylated ammoinium salt of DBU (3t’’)
consists 13% of the collected solids (Figure S7; for its mass spectrum, see Figures S3
and S4). According to the molar ratio and total amount, the recovery yield of
4-chloro-N-tosylbenzenesulfonamide was calculated to be 83% [(3.04 + 0.45)/4.2 ×
100%].
Characteristic peaks of the byproduct: For the anion, 1H NMR (400 MHz, CDCl3)
S-58
δ 7.59 (d, J = 8.2 Hz, 2H), 7.54 (d, J = 8.2 Hz, 2H), 7.15 (d, J = 8.5 Hz, 2H), 7.02 (d,
J = 8.5 Hz, 2H), 2.3 (s, 3H); For the protonated ammonium cation of DBU, 1H NMR
(400 MHz, CDCl3) δ 9.75 (brs, 0.87H, NH+); For the N-alkylated ammoinium cation
of DBU (the cation of 3t’’), 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 8.5 Hz, 0.13H,
ArH), 7.88 (d, J = 7.9 Hz, 0.13H, ArH), 7.78 (d, J = 8.2 Hz, 0.13H, ArH), 7.41 (t, J =
7.7 Hz, 0.13H, ArH).
9.749
7.973
7.953
7.894
7.875
7.794
7.774
7.605
7.585
7.571
7.549
7.528
7.426
7.409
7.388
7.299
7.277
7.183
7.166
7.144
7.033
7.012
4.039
4.022
4.006
3.609
3.594
3.578
3.512
3.488
3.472
3.458
3.423
3.407
3.390
2.825
2.647
2.635
2.621
2.355
2.324
2.046
2.031
2.018
2.003
1.988
1.737
1.732
1.653
1.584
1.097
-0.000
10 8 6 4 2 0 PPM
Figure S7. 1H NMR Spectrum of the Byproduct (400 MHz, in CDCl3)
10. Mechanistic Investigation on the Deoxyfluorination
of Alcohols with SulfoxFluor (1a)

10.1. Deoxyfluorination of Alcohol 2x with SulfoxFluor (1a)
S-59
A polytetrafluoroethylene (PTFE) NMR tube was charged sequentially with
SulfoxFluor (1a) (20.8 mg, 0.06 mmol), 2-(4-fluorophenyl)ethan-1-ol (2x) (7.0 mg,
6.3 μL, 0.05 mmol) and toluene (0.5 mL, 0.1 M), and then cooled to 0 oC. Upon DBU
(9.0 μL, 0.06 mmol) was added, the reaction was immediately monitored by NMR
instrument at room temperature. The yields of the intermediate 8x, alkyl fluoride 3x,
19
and 1-fluoro-4-vinylbenzene (3x’) were determined by F NMR spectroscopy
19
analysis. F NMR characteristic peaks of the compounds (282 MHz, toluene): 2x, δ
–118.23 (m, 1F); 8x (3x’’), δ –116.14 (m, 1F); 3x, δ –116.88 (m, 1F), –215.32 (m, 1F);
3x’, δ –117.90 (m, 1F).
Summary of Results:
Results showed that the esterification proceeded much faster than the following
fluorination, and the fluorination was nearly completed in 10 minutes (Figure S8).
S-60
3x
100% 3x'
90% 2x
80% 8x (3x'')
70%
60%
Yield (%)
50%
40%
30%
20%
10%
0%
0:00 2:24 4:48 7:12 9:36 12:00 14:24 16:48
t (min)
Figure S8. Deoxyfluorination of Alcohol 2x with SulfoxFluor (1a) (t = 0–15 min)
10.2. Deoxyfluorination of Alcohol 2x with PyFluor
PyFluor (17.8 mg, 0.11 mmol), 2-(4-fluorophenyl)ethan-1-ol (2x) (14.0 mg, 12.5 μL,
0.1 mmol) and toluene (0.5 mL, 0.2 M). Upon MTBD (28.8 μL, 0.2 mmol) was added,
the reaction was immediately monitored by NMR instrument. The yields of the
intermediate S10, alkyl fluoride 3x, and 1-fluoro-4-vinylbenzene (3x’) were
S-61
19 19
determined by F NMR spectroscopy analysis. F NMR characteristic peaks of the
compounds (282 MHz, toluene): 2x, δ –118.30 (M, 1F); S10 (S11), δ –116.66 (m, 1F);
3x, δ –116.88 (m, 1F), –215.33 (m, 1F); 3x’, δ – 118.08 (m, 1F).
Summary of Results:
Results showed that the esterification proceeded much faster than the
following fluorination, and the fluorination was very slow (Figure S9). Moreover, the
final yield of the elimination product was significantly higher than that with
SulfoxFluor (1a) (Figure S10).
3x
100%
90% 3x'
80%
2x
70%
60% S10 (S11)
yield (%)
50%
40%
30%
20%
10%
0%
0 10 20 30 40 50
t (min)
Figure S9. Deoxyfluorination of Alcohol 2x with PyFluor (t = 0–45 min)
S-62
3x
100%
90% 3x'
80%
2x
70%
S10 (S11)
60%
yield (%)
50%
40%
30%
20%
10%
0%
0 500 1000 1500 2000 2500 3000
t (min)
Figure S10. Deoxyfluorination of Alcohol 2x with PyFluor (t = 0–48 h)
10.3. Deoxyfluorination of Alcohol 2x with PBSF
PBSF (18.1 mg, 0.06 mmol), 2-(4-fluorophenyl)ethan-1-ol (2x) (7.0 mg, 6.25 μL,
0.05 mmol) and toluene (0.5 mL, 0.1 M). Upon DBU (9.0 μL, 0.05 mmol) was added,
the reaction was immediately monitored by NMR instrument. The intermediate S12
was different to identify as the peak of intermediate S12 and PBSF coincided, the
yields of alkyl fluoride 3x, and 1-fluoro-4-vinylbenzene (3x’) were determined by 19F
S-63
NMR spectroscopy analysis. 19F NMR characteristic peaks of the compounds (282
MHz, toluene): 2x, δ –118.30 (M, 1F); 3x, δ –116.88 (m, 1F), –215.33 (m, 1F); 3x’, δ
– 118.08 (m, 1F).
Figure S11. Deoxyfluorination of Alcohol 2x with PBSF (t = 0–20 min)
10.4. Determination of the Relative Reactivity of PyFluor, SulfoxFluor
and PBSF
To estimate the relative deoxyfluorination ability of PyFluor, SulfoxFluor and

PBSF, we made the following assumption:21
(1) The esterification reaction is a very rapid step;
(2) The fluoride anion and the ester intermediate are formed quantatively in a 1:1
ratio;
(3) The fluoride anion and the ester intermediate react slowly in a bimolecular
mannaer.
19
Based on above assumptions and the in-situ F NMR measurements, the rate
constants of the deoxyfluorination with PyFluor, SulfoxFluor and PBSF in the
presence of DBU or MTBD in toluene were roughly calculated by fitting to a second
order reaction profile according to the following function: f(t)=A-[A/(Akt+1)] in
S-64
Excel spreadsheets,21,22 where f(t) is the yield of the alkyl fluoride 3x at a given
reaction time, A is the calculated maximum yield of 3x, k is the second order rate
constant (in min−1), and t is the reaction time (in min).
PyFluor: A=0.579, k=0.00385 min−1 (R2 = 0.992)
SulfoxFluor: A=0.932, k=0.590 min−1 (R2 = 0.986)
PBSF: A=0.537, k=3.157 min−1 (R2 = 0.998)
Reagent Estimated rate constant (min−1) Relative rate

PyFluor 0.00385 1.0
SulfoxFluor 0.590 153
PBSF 3.157 820
The relative rates (krel) for PyFluor, SulfoxFluor and PBSF are: 1.0, 153 and 820,
respectively, which is consistent with the leaving ability of the corresponding
sulfonates or sulfonimidates.
11. References
1. D. W. Kim, H.-J. Jeong, S. T. Lim, M.-H. Sohn, Angew. Chem. Int. Ed. 2008, 47,
8404.
2. M. K. Nielsen, C. R. Ugaz, W. Li, A. G. Doyle, J. Am. Chem. Soc. 2015, 137,
9571.
3. B. S. C. Skillinghaug, J. Rydfjord, F. Svensson, M. Behrends, J. Sävmarker, P. J. R.
Sjöberg, M. Larhed, J. Org. Chem. 2014, 79, 12018.
4. R. Kowalczyk, A. J. F. Edmunds, R. G. Hall, C. Bolm, Org. Lett. 2011, 13, 768.
5. J.-H. Youn, R. Herrmann, Synthesis 1987, 72.
6. W. Ye, L. Zhang, C. Ni, J. Rong, J. Hu, Chem. Commun. 2014, 50, 10596.
7. L. Li, C. Ni, F. Wang, J. Hu, Nat. Commun. 2016, 7, 13320.
8. Q. Xie, C. Ni, R. Zhong, L. Li, J. Rong, J. Hu, Angew. Chem. Int. Ed. 2017, 56,
3206.
S-65
9. J. C. Judkins, P. Mahanti, J. B. Hoffman, I. Yim, A. Antebi, F. C. Schroeder,
Angew. Chem. Int. Ed. 2014, 53, 2110.
10. A. D. Averin, E. R. Ranyuk, N. V. Lukashev, A. K. Buryak, I. P. Beletskaya, Russ.
J. Org. Chem. 2009, 45, 78.
11. P. Warrick, W. H. Saunders, J. Am. Chem. Soc. 1962, 84, 4095.
12. M. K. Muthyala, S. Choudhary, K. Pandey, G. M. Shelke, M. Jha, A. Kumar,
Eur. J. Org. Chem. 2014 , 2014, 2365.
13. A. S. Henderson, J. F. Bower, M. C. Galan, Org. Biomol. Chem 2014, 12, 9180.
14. X.-L. Bu, L.-C. Hong, R.-T. Liu, J.-Q. Hong, Z.-X. Zhang, X.-G. Zhou,
Tetrahedron 2012, 68, 7960.
15. S. Iimura, K. Manabe, S. Kobayashi, J. Org. Chem. 2003, 68, 8723.
16. Q. Zhang, X.-Q. Kang, L. Long, L.-J. Zhu, Y.-H. Chai, Synthesis 2015, 47, 55.
17. C. D'Amore, F. S. D. Leva, V. Sepe, B. Renga, C. D. Gaudio, M. V. D'Auria, A.
Zampella, S. Fiorucci, V. Limongelli, J. Med. Chem. 2014, 57, 937.
18. I. Dlouha, J. Kvicala, O. Paleta, J. Fluorine Chem. 2002, 117, 149.
19. J.-J. Yin, D. S. Zarkowsky, D. W. Thomas, M. M. Zhao, M. A. Huffman, Org. Lett.
2004, 6, 1465.
20. N. Taniguchi, Eur. J. Org. Chem. 2010, 2670.
21. M. K. Nielsen, D. T. Ahneman, O. Riera, A. G. Doyle, J. Am. Chem. Soc. 2018,
140, 5004.
22. G. Kemmer, S. Keller, Nature Protocols, 2010, 5, 267.
S-66
8.00
7.98
3.85 7.96
7.94
7.59
2.03 7.57
2.00 7.36
144.83
7.34
12. NMR Spectra
142.86
7.26
140.95
138.27
130.27
129.88
128.45
127.60
S-67
77.48
77.16
76.84
3.09 2.44
21.81
7.98
7.96
7.93
3.88 7.91
2.00 7.60
7.58
2.04
7.34
144.56 7.32
143.42 7.26
138.63
131.52
131.31
130.20
129.74
129.50
127.11
S-68
77.39
77.07
76.75
3.11 2.43
21.67
74.07
8.47
1.98 8.45
8.28
2.00 8.26
1.91 7.95
7.93
-0.00
7.37
2.06 7.35
7.26
S-69
3.20 2.46
-0.00
74.00
152.04
-0.00
145.04
138.79
138.56
138.35
129.95
129.77
127.21
125.02
S-70
77.48
77.16
76.84
21.74
80.77
80.74
8.03
8.01
7.92
7.90
7.87
1.02 7.85
4.88 7.79
7.78
1.05 7.76
2.00 7.72
0.00 2.01 7.70
2.98 7.68
7.66
7.56
7.54
7.52
7.37
7.26
S-71
-97.84
-97.86
-98.48
-98.50
-99.54
-100.18
-97.84
-97.86
-98.48
-98.50
-99.54
-100.18
0.00
4.86
3.54
3.53
3.52
3.51
3.51
3.50
3.50
3.32
3.32
3.31
3.31
3.31
2.04
2.02
1.91
1.90
1.89
1.88
1.88 146.60
1.87
1.83 135.60
1.80 135.26
1.78 135.12
1.76 134.80
1.64 131.17
1.63 131.03
1.62 129.62
1.62 129.53
1.61 129.44
1.60 129.25
1.60 128.97
1.50 128.66
1.49 127.14
1.48 127.02
2.10 1.48 127.00
S-72
1.46 126.99
1.45 122.54
1.44 77.41
1.43 77.16
1.42 76.91
1.40 75.99
1.39 75.96
1.38 75.79
3.00 1.38 75.76
1.34 75.61
1.32 75.58
1.31
1.29
1.29
1.27
1.26
1.26
1.03 1.20
2.05 1.19
2.05 1.18
3.08 1.16
1.14
9.32 1.12
4.03 1.11
6.05 1.10
7.07 1.09
3.01 1.08
1.07
1.06
1.00
0.99
0.97
0.95
0.70
7.29
7.27
3.97 7.25
6.00 7.19
7.17
7.15
S-73
3.63
1.98 3.61 72.42
3.59
63.57
2.67 57.96
2.65 57.69
4.02 2.64
2.64 49.64
2.62 49.43
2.19 49.21
2.11 49.00
1.82
1.80 48.79
4.01 1.79 48.57
4.23 1.78 48.36
1.77 43.87
4.10 37.25
1.58
1.56 36.99
1.54 35.69
1.37 23.97
19.20
12.52
-0.00
7.26
7.15 142.50
2.00
7.13
2.00 6.87
6.85
128.51
128.37
125.88
S-74
4.11
4.10
2.03 4.08 77.48
2.02 3.86 77.16
3.84 76.84
3.83 74.30
3.00
2.97 62.72
1.02 2.97
2.96
2.94
4.02 2.50
2.19 2.49
2.48
0.96 2.47 41.23
2.10 2.46 39.12
2.07 2.19
2.19 32.66
2.17 30.08
2.16 26.44
2.15 23.40
2.12
2.04
2.03
2.01
1.91
1.89
1.86
-0.01
211.38
157.45
7.10
1.98 7.08
2.00 6.83
6.81
137.11
127.59
114.59
2.01 4.86
S-75
4.04
4.03
4.02
3.74
2.08 3.73
2.02 3.72 77.40
3.59 77.08
0.98 76.76
3.58
3.57
3.32 65.76
3.31
3.31 60.38
2.42
2.41
1.00 2.40
2.39
2.03 41.90
2.04 2.04
41.36
2.02
2.06 2.01 34.17
1.98 32.04
4.11 1.97
1.96
1.95
1.85
1.83
1.82
1.51
1.50
1.48
1.43
1.42
1.40
1.37
7.14
7.13
6.66
6.64
6.64
6.58
4.51
4.50
4.49
4.48
3.97
3.96
3.94
3.55
3.54
3.53
3.51 156.83
3.49
3.33
2.75
1.00 2.74
2.50
2.26 138.66
1.01 2.26
1.01 2.23
2.23 127.45
2.10
2.10
2.08
2.06
114.15
1.90
1.89
1.88
1.87
1.84
1.83
S-76
1.82
2.01 1.81
1.79
1.78
1.77
2.07 1.60
1.58
1.58
2.98 1.57 68.70
1.55
64.44
1.39
1.38
1.36 57.35
2.01 1.34 42.10
1.33 40.15
1.33 39.94
1.30 39.73
1.07 1.28 39.52
1.05 1.26 39.31
4.96 1.25 39.10
1.07 1.23 38.89
1.22 35.83
7.26 1.21 32.51
1.19 32.18
1.19
1.17
2.98 1.16
1.14
1.13
1.12
1.11
1.10
1.09
0.66
7.26 156.40
7.07
7.07
7.05
7.05
1.96 6.80
6.80
1.98 6.79 137.33
6.78 132.06
6.78 126.06
6.77
114.07
111.92
S-77
3.93
3.92 80.02
2.02 3.90
3.66
2.00 3.64
3.63
64.35
2.81
2.04 2.79 57.37
2.01 2.72
2.70 49.51
2.69 43.49
2.11 42.78
3.96 1.80 40.14
2.05 1.78 39.93
2.05 1.77 39.72
1.63 39.52
2.03 1.62 39.31
1.62 39.10
1.60 38.89
1.59 38.57
1.55 32.19
1.54 29.88
1.53 11.22
1.52
1.52
1.50
-0.01
208.48
HO
13
O
S8
157.39
C NMR (CDCl3, 100 MHz)
7.26
O
7.10
2.00 7.08
6.82
2.05 6.80
132.85
129.18
114.48
S-78
3.94
3.93
2.09 3.91 77.43
3.66 77.11
2.05
3.65 76.80
3.63
67.80
62.62
2.62
2.61
1.97 2.60
2.59
2.58
45.43
2.00 1.85
2.30 1.79
1.77 32.37
2.02 30.10
1.74
2.19 1.69 29.04
4.03 1.61 28.87
2.96 1.55 22.34
2.95 1.53
1.52
1.20
0.94
0.92
0.90
0.00 0.00
7.82
7.79
7.77
7.64
1
7.48
7.47
7.46
7.45
7.44
7.44
7.42
3b
7.42
7.40
7.40
7.35
F
7.35
2.83 7.33 157.20
0.98 7.33
H NMR (CDCl3, 400 MHz)

1.88 4.77
0.99 4.76
4.76
4.75
4.75
4.74 134.68
4.65
4.64 129.22
4.63
4.63
4.63
4.62
114.54
3.00
2.99
2.98
2.96
2.95
2.94
S-79
0.57 2.93
0.58 2.90
2.88
2.87
2.86
2.85 77.48
2.84 77.16
2.84 76.84
2.82 72.95
2.10 67.92
2.09 62.63
1.11 2.08
1.10 2.08
2.06
2.06
2.05
2.04 43.48
1.17 2.03
1.18 1.96
1.96 34.41
1.95 32.45
1.57 1.93 29.42
1.54 1.91 29.13
1.90 26.35
1.88 22.42
1.88
1.88
1.87
1.86 8.34
1.40
1.38
1.34
1.32
0.00
19
13
3b
3b
F
F
F NMR (CDCl3, 376 MHz)

138.96
133.61
132.02
-174.07 128.01
-174.12 127.61
-174.14 127.41
-174.16 127.23
-174.18 126.50
-174.20 125.97
-174.22 125.23
-174.24
-174.27
-174.28
-174.31
-174.33
-174.33
-174.35
S-80
-174.37 90.85
-174.39 89.21
-174.41
-174.44
-174.45 -174.07 77.34
-174.48 -174.12 77.02
-174.52 -174.14 76.70
-174.16
-174.18
-174.20
-174.22
-174.24
-174.27
-174.28
-174.31
-174.33
-174.33
-174.35 38.64
-174.37 38.43
-174.39 31.53
-174.41 31.48
-174.44
-174.45
-174.48 21.15
-174.52 20.92
-0.00
8.06
8.05
7.88
7.87
7.87
7.74
7.73
7.55
7.55
7.53
7.53
7.53
7.52
7.52
0.99 7.51
0.93 7.50
0.92 7.49
1.83 7.48
7.48
0.94 7.43
138.17 0.96 7.42
133.89 7.40
131.82 7.35
128.78 7.33
126.65 7.26
125.96 4.77
125.77 4.77
125.50 4.76
125.44 4.76
123.73 4.67
4.67
4.66
4.66
4.66
3.14
0.55 3.13
S-81
3.11
91.68 0.54 1.98
90.04
1.97
1.96
1.96
77.33
1.95
77.02
1.95
76.70
1.94
1.88
1.87
2.02 1.87
1.86
1.85
1.85
1.84
1.83
1.83
1.82
36.94 1.81
36.74 4.31 1.81
32.74 1.81
26.23 1.50 1.80
26.19 1.49 1.79
21.15 1.79
20.92 1.72
1.70
1.67
1.66
1.65
1.37
-0.00 1.36
1.32
1.31
0.03
7.48
7.46
7.44
7.43
1.90 7.42
1.93 7.40
7.37
0.94 7.35
2.05 7.33
2.05 7.26
7.14 -172.28
7.12 -172.32
6.95 -172.34
6.93 -172.38
-172.41
-172.45
-172.47
-172.51
-172.53
-172.55
-172.58
2.12 5.07
-172.59
0.48 -172.61
S-82
0.48 -172.64
-172.65
-172.67
-172.72
-172.28
-172.32
-172.34
-172.38
2.64 -172.41
2.03 2.62 -172.45
2.60 -172.47
-172.51
1.81 -172.53
1.80 -172.55
1.78 -172.58
4.38 1.72 -172.59
1.59 1.71 -172.61
1.92 1.70 -172.64
1.69 -172.65
1.69 -172.72
1.67
1.67
1.38
1.36
1.32
1.30
0.05
-0.00
157.03
-172.73 137.22
-172.78 134.48
-172.80 129.29
-172.81 128.54
-172.84 127.87
-172.86 127.46
-172.87
-172.91
-172.92 114.72
-172.93
-172.94
-172.97
-172.98
-172.99
-173.00
S-83
-173.04 91.66
-173.05 90.02
-173.07
-173.11
-173.13 77.34
-173.17 -172.73 77.03
-172.78 76.71
-172.80 70.04
-172.81
-172.84
-172.86
-172.87
-172.91
-172.92
-172.93
-172.94
-172.97
-172.98
36.48
-172.99
36.27
-173.00
34.71
-173.04
-173.05 27.06
-173.07 27.01
-173.11 21.11
-173.13 20.88
-173.17
0.00
7.26
7.14
7.12
6.86
6.84
4.75
4.74
4.73
4.73
4.72
4.72
4.71
4.70
4.62
4.61
157.86 4.61
4.60
4.60
4.59
4.59
2.00 4.58
3.80
1.98 2.79
133.53 2.78
2.76
129.33 2.75
2.74
2.73
2.72
2.69
113.84 2.67
2.66
2.65
2.65
2.63
2.63
S-84
0.52 2.61
90.86 0.52 2.00
89.22 1.98
1.98
1.97
77.36
1.96
77.04 3.14 1.95
76.72
1.95
1.94
1.92
1.87
1.86
1.01 1.85
55.25
1.84
1.08 1.83
1.82
1.80
39.01 1.79
1.10 1.78
38.80
1.41 1.77
30.46 1.76
30.42 1.46 1.76
1.53 1.75
21.12 1.74
20.90 1.73
1.70
1.70
1.69
1.69
1.39
0.00 1.37
1.33
1.31
0.02
19
MeO
7.84
7.82
7.81 3e
7.80
7.79
7.64
7.50
F
7.50
2.89 7.48
0.98 7.48
7.46
1.88
7.46
0.97 7.44
7.44
7.43 -174.05
7.42 -174.09
7.37 -174.12
7.37 -174.13
7.35 -174.16
7.34 -174.18
7.26 -174.20
-174.22
-174.24
-174.24
-174.26
-174.29
-174.30
-174.31
4.54 -174.33
S-85
4.52 -174.35
1.00 4.51 -174.37
1.00 4.42 -174.39
4.41 -174.41
4.39 -174.05
-174.43
-174.09
-174.45
-174.12
-174.50
-174.13
-174.16
-174.18
-174.20
2.84 -174.22
2.11 2.82 -174.24
2.80 -174.24
-174.26
-174.29
1.82 -174.30
1.82 -174.31
1.80 -174.33
4.22 1.78 -174.35
1.77 -174.37
2.24 1.76 -174.39
1.75 -174.41
1.74 -174.43
1.73 -174.45
1.72 -174.50
1.55
1.54
1.53
1.51
1.49
0.04
139.95
133.67
132.02
127.88
127.65
-217.83 127.45
127.37
126.40
-217.90 125.93
125.13
-217.96
-217.97
S-86
-218.03
-218.08 84.94
-218.09 83.31
77.40
77.08
-218.15 76.77
-218.22
36.00
31.00
30.46
30.26
-217.83
24.97
-217.90
-217.96 24.92
-217.97
-218.03
-218.08
-218.09
-218.15
-218.22
0.06
13
Ph
7.63
7.63
3g
7.61
7.58
7.56
2.00 7.49
2.00 7.47
7.45
F
1.98
7.39

0.96 7.38
141.00 2.00 7.37
140.22
7.35
139.06
7.35
128.91
128.74 7.32
127.21 7.30
7.26
127.10
127.00
4.60
S-87
4.58
1.03 4.57
1.03 4.48
83.94 4.46
82.30 4.45
77.34
77.02
76.71
2.85
2.12 2.83
2.81
2.15
2.13
2.11
2.08 2.11
2.09
32.11 2.08
31.91 2.07
30.99 2.05
30.94 2.05
2.03
2.01
0.00 0.05
-0.00
7.26
-220.30
-220.37
4.49 -220.43
S-88
4.48 -220.44
0.92 4.47
0.92 4.40 -220.49
4.39 -220.50
4.37
-220.56
1.73 -220.57
1.71
1.71 -220.62
1.70
1.68
1.66 -220.69
1.66
1.65
1.41
1.40
1.39
1.38
1.36
1.33
1.90 1.32
2.03 1.30
24.50 1.29 -220.30
1.26 -220.37
0.90 -220.43
2.92 0.88 -220.44
0.87 -220.49
-220.50
-220.56
-220.57
-220.62
0.00 -220.69
19
3h
14
F

-217.83
-217.89
-217.95
-217.96
-218.02
S-89
-218.08 85.07
-218.09 83.44
77.35
-218.15 77.03
76.71
-218.21
31.96
30.55
30.35
29.73
29.70
29.68
29.59
29.56
29.40
29.29
25.20
-217.83 25.15
-217.89 22.73
-217.95 14.14
-217.96
-218.02
-218.08
-218.09
-0.00
-218.15
-218.21
7.39
7.38
7.35
7.33
7.33
18.00
7.32
138.36 2.04 7.32
137.97 7.26
137.94 7.21
137.79 7.20
7.19
128.50
128.47
128.21 4.96
127.99 4.94
127.94 4.92
0.09
127.89 4.89
111.00 1.00
4.87
108.85 0.12
4.85
1.02
4.82
1.18
4.77
83.58 2.13
4.74
83.47 1.15
S-90
4.69
81.65 1.06
4.66
81.44 2.16
4.60
77.44 0.10
4.57
77.12 4.06
76.99 4.04
0.23
76.80 4.02
4.25
75.48 3.99
2.06
75.02 3.95
74.94 3.80
74.90 3.78
74.48 3.76
74.46 3.74
73.65 3.72
68.48 3.70
3.68
3.66
3.65
3.63
3.61
3.58
0.06
7.26
4.86
4.74
2.46
2.43
2.41
2.39
2.10
2.08
2.06
2.03
2.01
1.96
1.94
1.93
1.93
1.92
1.91
1.90
1.89
1.87
1.80
1.79
1.78
1.77
1.77
1.69
1.68
1.65
1.63
1.62
1.61
1.59
1.57
1.56
0.97 1.55
S-91
1.53
1.52
1.51
1.51 -137.89
1.50 -137.92
1.48 91.5 -138.03
1.48 -138.06
1.46 -149.36
1.45 8.5 -149.43
1.43 -149.50
1.42 -149.57
1.39
1.34
1.33
1.31
1.30
1.02 1.28
1.03 1.28
2.11 1.26
2.05 1.26
1.25
8.04 1.24
6.29 1.24
1.11 1.22
7.00 1.03
1.02
1.00
0.99
0.85
0.83
0.80
0.78
0.77
-0.01
221.33
-180.94
-180.98
-181.01
-181.07
-181.10
-181.12
-181.14
S-92
-181.19
-181.22
-181.25
-181.32 90.14
-181.35 88.49
-181.38
77.37
77.06
76.74
-180.94 54.22
-180.98 51.45
-181.01 47.79
-181.07
-181.10 39.40
-181.12 35.88
-181.14 35.85
-181.19 35.03
-181.22 32.38
-181.25 31.55
-181.32 30.77
-181.35 28.05
-181.38 21.75
20.06
13.83
11.16
-0.00
7.26
5.60
5.60
5.59
5.58
5.57
2.47
2.44
2.42
2.40
2.08
2.06
2.03
2.01
1.97
1.96
1.95
1.94
1.92
1.92
7.26
1.91
1.90
1.87
1.83
1.82
1.81
1.80
1.80
1.79
1.78
1.77
1.80 1.73
1.71
1.69
4.47 1.65
4.46 1.63
S-93
4.44 1.63
0.93 4.37 1.60
0.93 4.36 1.59
4.35 1.53
3.97 1.52
5.42 1.51
3.97
1.50
1.50
1.49
1.47
1.46
1.46
1.40
1.39
2.44 1.37
2.02 2.43 1.00 1.36
2.41 1.33
2.91 4.07 1.29
1.99 1.27
1.69 2.05 1.26
2.07 1.67 3.35 1.24
1.64 5.04 1.23
14.00 1.38 3.38 1.21
1.37 1.20
1.08
1.36 0.99
1.35 3.17 0.98
1.33 3.97 0.86
1.32 0.85
1.31 0.80
1.30 0.79
1.27 0.77
-0.02
0.76
0.75
-0.01
0.00 184.72
184.16
144.31
144.30
143.07
138.68
-218.28
S-94
-218.34
85.04
83.41
-218.40
77.40
77.08
76.76
-218.47
-218.54
61.15
-218.60
-218.66 30.51
30.31
29.81
29.46
29.39
29.34
29.21
-218.28 28.73
-218.34 26.40
-218.40 25.17
-218.47 25.11
-218.54 11.91
-218.60
-218.66
-0.00
7.82
7.82
7.80
7.78
7.71
7.61
7.61
7.59
7.59
7.49
7.48
7.48
2.97 7.46
7.46
1.01 7.44
1.03 7.44
134.95 1.91 7.43
133.66 7.42
132.74 7.26
130.94 6.64
129.64 6.60
128.10
1.00 6.40
127.85 1.01 6.38
127.62 6.36
126.18 6.36
125.58 6.34
125.54 6.32
123.47
4.62
S-95
4.61
1.00 4.59
1.00 4.50
84.18 4.49
82.54 4.47
77.34
77.03
76.71
2.45
2.45
2.43
2.42
2.09 2.40
2.40
2.00
2.04 1.98
1.98
30.19 1.97
29.99 1.96
28.73 1.95
28.68 1.94
1.93
1.92
1.92
1.90
1.90
1.88
1.87
-0.00
0.00
7.92
7.81
7.80
7.80
7.79
7.78
7.78
7.77
0.93 7.75
2.99 7.50
2.87 7.50
7.49
7.48
7.47
7.47
7.47
7.46
7.45
7.44
7.26
-219.79
-219.86
-219.92
4.72 -219.93
4.71
S-96
1.00 4.70 -219.99
1.00 4.61
4.59 -220.05
4.58 -220.06
-220.11
-220.18
2.65
2.03 2.63
2.61
2.10
2.09
2.04 2.08
2.07
2.06
2.05
2.04
-219.79
2.02
2.02 -219.86
-219.92
2.01
-219.93
1.99
-219.99
1.99
1.97 -220.05
-220.06
-220.11
0.01 -220.18
0.00
133.05
132.58
131.20
128.65
127.91
127.74
127.63
126.47
126.41
121.00
-221.75
S-97
-221.82 88.90
-221.88 83.44
-221.89 81.80
-221.95 81.65
-222.00 77.39
-222.02 77.07
-222.07 76.75
-222.14
29.76
29.56
-221.75
-221.82
-221.88 15.60
-221.89 15.55
-221.95
-222.00
-222.02
-222.07
-222.14
7.70
7.70
7.69
7.68
7.68
7.67
7.67
7.66
7.66
7.65
7.26
5.20
5.20
5.20
5.19
5.19
5.10
3.95 5.09
5.08
3.57
3.56
3.55
135.74 3.54
132.41 3.53
128.97 3.53
127.93 3.51
3.49
3.49
3.49
3.48
3.48
3.45
3.28
0.50 3.27
0.50 3.26
3.26
S-98
92.98 3.25
91.20 3.25
3.24
3.23
2.20
77.37
2.19
77.05
2.18
76.74
2.09 2.17
1.07 2.16
2.16
1.05 2.16
2.15
54.53 2.15
54.30 2.13
2.13
2.12
45.90
1.05 2.12
2.03
1.08 2.03
32.65 2.02
32.43 2.01
2.01
2.00
1.99
1.99
1.95
1.94
1.93
1.93
1.92
0.00 1.91
1.91
1.90
-0.01
10.03
7.92
0.95 7.90
7.68
7.66
7.63
7.61
7.26
5.40
5.39
5.38
-0.00
5.26
5.13
3.99
3.95
1.97 3.92
3.89
1.95 3.88
3.87
3.84
3.83
3.81
3.80
3.79
3.77
3.76 -176.25
3.75 -176.30
3.70 -176.33
3.69 -176.35
3.67 -176.38
3.66 -176.39
3.65 -176.40
3.63 -176.41
1.00 -176.44
3.61
3.58 -176.46
3.55 -176.48
S-99
3.54 -176.49
3.52 -176.49
3.50 -176.52
3.47 -176.54
2.38 -176.55
2.36 -176.57 -176.25
2.12 -176.58 -176.30
2.34
2.33 -176.60 -176.33
2.11 -176.62 -176.35
2.30
2.29 -176.63 -176.38
2.26 -176.66 -176.39
2.25 -176.71 -176.40
2.23 -176.41
2.21 -176.44
2.15 -176.46
2.14 -176.48
1.07 2.11 -176.49
2.10 -176.49
1.29 -176.51
2.09
2.07 -176.52
2.07 -176.54
2.04 -176.55
2.04 -176.57
2.03 -176.58
2.01 -176.60
2.00 -176.62
1.99 -176.63
1.98 -176.66
1.97 -176.71
1.95
1.94
1.94
1.93
-0.04
191.56
-0.00
168.82
168.59
142.04
141.88
137.26
137.19
129.85
-176.25 129.78
-176.30 127.83
-176.33 127.70
-176.35
-176.38
-176.39
-176.40
-176.41
-176.44
-176.46
-176.48
-176.49 93.28
S-100
-176.49 92.33
-176.52 91.50
-176.54 90.58
-176.55
-176.57 -176.25 77.44
-176.58 -176.30 77.12
-176.60 -176.33 76.80
-176.62 -176.35
-176.63 -176.38
-176.66 -176.39
-176.71 -176.40
-176.41 55.51
-176.44 55.28
-176.46 53.11
-176.48 52.88
-176.49 46.90
-176.49 44.07
-176.51
-176.52 33.20
-176.54 32.98
-176.55 31.16
-176.57 30.94
-176.58
-176.60
-176.62
-176.63
-176.66
-176.71
0.00
7.37
7.36
154.84 7.34
154.71 7.34
7.33
4.40 7.33
7.32
7.31
7.31
136.76 7.30
128.49 7.30
128.01 7.26
127.94
5.30
5.29
0.51 5.28
5.19
2.50 5.16
93.74 5.15
5.12
S-101
92.91
91.98
91.15 3.72
3.69
3.67
77.38 3.64
77.06 3.62
76.74 4.11 3.56
3.55
66.92 3.53
3.52
3.51
53.01 3.50
52.78 2.29
52.65 2.27
52.41 2.25
43.98 1.03 2.24
43.63 2.21
1.12 2.19
32.59 2.07
32.37 2.06
31.83 2.04
31.61 2.03
2.01
2.00
1.96
1.95
1.94
1.93
1.90
1.89
0.00 0.00
1
Boc
N
F
3q
CO2Me
-176.98

-177.03
7.26
-177.04
-177.08
-177.09 -177.09
-177.12 -177.12
-177.14 -177.12
-177.14 -177.14
-177.15 -177.14
-177.19 -177.15
-177.20 -177.17
-177.22 -177.19
-177.23 -177.20
-177.27 -177.22
5.24 -177.28 -177.23
1.09 -177.28 -177.25
5.11
-177.29 -177.27
-177.30 -177.28
S-102
4.53 -177.33 -177.28
4.50 -177.52 -177.29
1.01 4.41 -177.30
-177.55
4.39 -177.62 -177.33
-177.63 -177.34
0.92 3.83 -177.38
-177.64
3.79 -177.39
3.02 -177.66
3.76 -177.40
1.02 -177.72
3.72 -177.44
-177.76
3.70 -177.45
3.67 -177.47
3.58 -177.50
2.50 -177.52
2.46 -177.54
2.45 -177.55
2.24 2.45 -177.56
2.41 -177.57
2.39 -177.58
2.38 -177.59
2.37 -177.62
2.36 -177.63
9.00 2.35 -177.64
2.34 -177.66
2.33 -177.68
2.32 -177.69
2.30 -177.70
2.29 -177.71
2.28 -177.72
2.27 -177.73
2.26 -177.76
2.25 -177.77
-0.03
-177.80
-177.82
-177.87
172.30
171.91
154.04
153.67
-172.84
-172.86
-172.91
-172.93
-172.95
-173.00 -172.70
-173.02 -172.75
-173.07 -172.77
-173.09 -172.79
-173.11 -172.80
-173.13 -172.82
-173.16 -172.84
-173.18 -172.86
-173.20 -172.88
-173.22 93.11
S-103
-172.89 92.04
-173.23 -172.90
-173.25 91.35
-172.91 90.28
-173.27 -172.93
-173.29 80.44
-172.95 80.40
-173.31 -172.96
-173.32 77.40
-172.97 77.09
-173.34 -172.98
-173.36 76.77
-173.00
-173.02 57.65
-173.04 57.26
-173.05 53.32
-173.07 53.08
-173.09 53.00
-173.11 52.75
-173.13 52.38
-173.14 52.24
-173.16 37.58
-173.18 37.36
-173.20 36.72
-173.22 36.50
-173.23 28.39
-173.25 28.27
-173.27
-173.29
-173.31
-173.32
-173.34
-173.36
-173.38
-173.39 0.00
-173.41
-173.43
-173.48
1
13
N
N
3r
1.96 8.54
3r
F
F
150.13
149.76 7.26

7.14
2.01 7.14
124.06
4.51
S-104
4.50
1.00 4.48
83.51 1.00 4.41
81.86 4.40
77.38 4.39
77.06
76.74
2.76
2.04 2.74
2.73
2.07
2.05
2.10 2.05
2.04
31.01
2.04
30.81
2.04
30.76
2.02
2.01
2.01
2.00
2.00
1.99
1.99
1.98
0.00 1.97
-0.01
19
N
3r
7.33
7.31
F
7.30
1.90 7.29
2.87 7.26
7.24
7.22
7.20
4.97
4.95
-220.70
4.94
0.53 4.84
0.52 4.83
S-105
4.81 -220.77
4.27
4.25 -220.82
2.01
4.23 -220.84
4.21
-220.89
2.83 -220.95
2.82 -220.96
2.81
2.80
2.03 -221.02
2.79
2.78
2.27 -221.09
2.20 2.25
2.23
2.23
2.19
2.17
1.32
3.05 1.30 -220.70
1.29 -220.77
-220.82
-220.84
-220.89
-220.95
-220.96
-221.02
0.01 -221.09
-0.00
169.99
169.75
140.20
128.57
128.54
126.32
-193.64
-193.71
S-106
88.96
-193.78 87.12
77.37
77.05
76.73
-193.84
61.51
-193.91
-193.64 34.18
-193.71 33.97
-193.78 30.53
-193.84 30.50
-193.91
14.16
0.00
8.05
8.03
7.90
7.88
7.80
7.78
7.58
7.58
7.57
1.00 7.56
0.94 7.56
7.54
0.95 7.54
1.90 7.54
1.90 7.53
133.87 7.52
132.82 7.51
132.74 7.50
131.99 7.50
128.89 7.47
127.56 7.45
127.17 7.43
126.18 7.42
125.66 7.40
125.53 7.26
123.34
4.86
4.85
1.05 4.83
4.75
S-107
1.05
4.73
84.35 4.71
82.67
77.34
77.02 3.57
76.70 3.55
3.53
2.14 3.52
3.50
3.48
33.93
33.72
-0.00 0.03
1
MeO
MeO
3u
F
7.26

6.83
6.81
2.84 6.78
6.78
6.76
-213.23
-213.24
-213.29
-213.29
S-108
1.00 4.66
1.02 4.55 -213.34
-213.36
-213.41
3.88 -213.42
6.06 3.86 -213.47
-213.47
-213.48
3.00
-213.54
2.99
-213.54
2.97
1.99 2.94 -213.59
2.93 -213.60
2.91
-213.23
-213.24
-213.29
-213.29
-213.34
-213.36
-213.41
-213.42
-213.47
-213.47
-213.48
-213.54
-213.54
-0.00 -213.59
-213.60
13
19
MeO
MeO
MeO
MeO
3u
3u
F
F
-0.00

148.94
147.83
129.70
129.64
-215.30 120.91
112.22
-215.36 111.31
-215.42
S-109
-215.48
85.15
-215.55 83.47
77.39
77.07
-215.61 76.75
-215.67
55.91
55.84
-215.30
-215.36 36.62
-215.42 36.42
-215.48
-215.55
-215.61
-215.67
-0.00
13
1
N
N
S
S
3v
3v
F
F
150.08

150.05
0.96 8.60
125.82
7.26
S-110
83.92 4.65
82.23 4.63
77.37 1.00 4.62
77.06 0.98 4.53
76.74 4.52
4.50
3.20
3.19
3.17
1.96 3.14
3.13
3.11
3.08 2.41
27.73
27.51
14.89
-0.01
0.00
1
19
N
O
S
3v
3w
7.58
7.57
7.54
7.51
F
F
7.49
7.34
7.34

2.95 7.33
7.33
1.88 7.31
7.31
7.29
7.29
7.27
7.27
7.27
7.26
-215.26
-215.32
4.78 -215.38
4.77
1.10 4.76
S-111
1.09 4.69 -215.44
4.68
4.66
-215.51
3.14
3.14
-215.57
3.13
3.12
3.11
-215.63
1.10 3.11
1.09 3.09
3.09
3.08
3.08
3.07
3.06
-215.26
-215.32
-215.38
-215.44
-215.51
-215.57
-215.63
0.03
13
19
0.00
O
3w
3w
F
F
155.28

142.21
142.20
127.88
124.39
122.51
119.43
-214.84
115.84
115.78
-214.90 111.55
-214.96
S-112
-215.02
83.60
-215.09 81.92
77.35
77.03
-215.15 76.71
-215.21
-214.84 25.19
-214.90 24.97
-214.96
-215.02
-215.09
-215.15
-215.21
0.00
162.92
160.97
7.26
7.22
7.20
1.95 7.20
1.83 7.18
7.03
7.01
130.57 6.99
130.51
115.58
115.41
4.69
4.69
4.67
4.67
4.66
S-113
1.00 4.65
1.00 4.57
84.80 4.57
83.46 4.55
77.41 4.55
77.16 4.54
76.91 4.54
3.04
3.02
1.01 3.00
0.99 2.98
2.96
2.94
36.35
36.18
0.01
-0.00
-216.18
-116.99
-216.24
-117.00
7.26 -216.31 -117.01

7.12
2.01 7.10
6.84 -216.37 -117.03
2.01
6.82
-216.43 -117.04
-117.05
-216.49
-117.06
-216.56
4.72
4.70
4.69 -116.99
1.00 4.60
S-114
-117.00
1.00 4.59 -117.01
4.57 -117.03
-117.04
2.08 4.09 -117.05
4.07 -117.06
0.99
4.06
3.82
3.81
3.79
2.68
2.66
2.12 2.63
2.63
2.61
2.03 2.21
2.19
2.18
2.24 2.14
0.83 2.13
3.10 2.11
1.76 -216.18
1.75 -216.24
1.74 -216.31
1.73 -216.37
1.73 -216.43
1.71 -216.49
1.23 -216.56
1.21
0.00
-0.00
156.96
134.32
129.31
114.47
-222.48
-222.55
S-115
-222.61
-222.62
-222.68 81.64
80.00
77.35
-222.73
77.03
-222.75
76.71
-222.80 67.51
63.55
63.50
-222.87
41.06
31.22
30.58
30.38
-222.48 23.63
-222.55
-222.61
-222.62
-222.68
-222.73
-222.75
-222.80
-222.87 0.00
7.26
4.46
4.45
4.44
4.37
4.36
4.34
3.61
1.97
1.95
1.85
1.84
1.83
1.81
1.80
1.80
1.79
1.78
1.77
1.76
1.74
1.72
1.66
1.65
1.64
1.58
1.57
1.56
1.55
1.51
1.51
1.50
1.49
1.48
1.48
1.42
S-116
1.40
0.96 1.39
1.39
85.54 0.95 1.38
83.90
1.37
77.36 1.37
77.04 1.36
76.72 0.97 1.33
71.86 1.25
1.25
1.24
1.23
56.51 1.21
56.10 1.21
1.14
42.10 1.13
40.45 1.13
40.20 1.04 1.11
35.85 4.04 1.11
35.42 3.46 1.10
34.58 4.09 1.10
27.21 1.09
6.08
26.43 1.07
24.21 0.96 1.06
23.38 3.53 1.05
20.83 7.00 1.04
18.53 6.20 1.04
12.05
2.96 1.03
0.96
0.96
-0.00 0.92
0.91
0.64
-0.01
7.26
4.65
4.64
4.63
4.62
4.58
4.58
4.57
4.57
4.56
4.55
0.00
4.55
4.53
4.52
4.49
4.48
4.48
4.47
3.80
3.79
3.78
3.77
3.77
3.69
3.68
3.67
1.62
1.61
1.60
1.59
1.55
1.54
1.54
1.53 -217.58
1.53
1.53 -217.65
S-117
1.52
2.04 1.51
-217.71
1.50
1.50
1.49 -217.77
1.49
0.50 1.48
0.46 -217.84
1.47
1.46
1.45 -217.90
1.44
1.43
-217.96
1.43
1.41
1.38
1.37
1.36
1.36
1.36
1.35
2.09 1.35
6.38 1.34
1.34
1.33 -217.58
6.00 1.32 -217.65
0.98 -217.71
0.97 -217.77
0.96 -217.84
0.95 -217.90
0.95 -217.96
0.94
0.94
0.93
-0.01
0.00
-226.17
-226.18
-226.24
-226.30
-226.31
-226.37
-226.37
85.34
S-118
-226.43
-226.43 84.62
-226.49 83.69
-226.50 82.98
77.36
77.04
76.73
71.94
71.90
71.83
-227.91 71.79
-227.98
-228.04
-228.11
-228.16 46.34
-228.24 46.26
46.18
-226.17 46.09
-226.18 37.26
-226.24 36.22
-226.30
-226.31 20.39
-226.37 20.33
-226.37 19.47
-226.43 19.19
-226.43 18.06
-226.49 17.99
-226.50 14.06
-227.91 12.20
-227.98 11.72
-228.04 -0.00
-228.11
-228.16
-228.24
7.34
7.32
7.31
3.81 7.31
5.73 7.26
142.36
7.24
7.22
7.20
128.48
128.32
125.87
4.56
4.54
S-119
1.00 4.53
84.89 1.00 4.44
83.26 4.42
77.35 4.41
77.03
76.72
74.23
2.72
2.71
4.07 2.70
2.69
2.68
41.24 1.88
39.07 4.14 1.87
1.86
30.48 2.14 1.85
30.28 2.14 1.83
30.03 5.02 1.79
25.88 1.73
25.83 1.71
23.26 1.64
1.62
1.61
1.47
1.46
1.45
-0.00 0.04
-0.00
7.26
7.12
2.01 7.10
2.00 6.85
6.83
F
-218.36
1
-218.43
O
4.71 -218.49
4.70
7e
4.68
0.97 4.60
S-120
-218.56
0.97 4.58
4.57
2.05 4.07 -218.62

4.06
OH
0.98 3.69
-218.68
3.68
3.67
3.66
3.65 -218.75
2.20
2.19
2.17
0.99 2.14
2.12
4.04
2.11
1.98 2.07
1.65 1.89
3.87
1.57
1.55
1.51 -218.36
1.48 -218.43
1.45 -218.49
1.43 -218.56
1.41 -218.62
1.40 -218.68
1.36 -218.75
1.26
0.00
F
19
O
0.00
7e
157.04

OH
138.94
-222.54 127.65
-222.61
114.35
-222.66
-222.73
S-121
-222.79
-222.80 81.63
79.99
77.34
-222.86 77.03
76.71
70.67
63.49
-222.92 63.43
42.52
35.96
32.65
30.56
30.36
-222.54
-222.61
-222.66
-222.73
-222.79
-222.80
-222.86
-222.92 0.00
7.26
7.22
7.20
6.73
6.72
6.71
6.70
6.65
6.64
4.70
4.69
4.68
4.60
4.59
4.58
4.09
156.63 4.07
4.06
3.75
3.73
1.00 3.72
2.86
138.06 2.85
0.99 2.84
132.89 0.95 2.33
2.31
126.38 2.30
2.19
2.18
114.52 2.17
112.02 2.14
2.13
2.12
2.12
2.10
1.97
1.07
S-122
1.95
1.01 1.94
81.91 1.90
81.69 1.88
80.05 2.05 1.70
77.38 1.58
77.06 1.08 1.51
76.74 1.51
1.50
63.47 1.49
63.41 1.49
1.48
2.19 1.46
1.45
50.05
1.43
43.97 1.15 1.43
43.28
4.00 1.41
38.86
1.12 1.39
36.73
1.07 1.38
30.60
1.36
30.41 1.19 1.36
29.81 1.34 1.35
27.26
6.25 1.34
26.34
1.10 1.33
23.15
1.32
2.85 1.31
1.30
11.08 1.29
1.23
1.21
1.21
1.20
1.19
0.78
F
F
1
19
O
O
-0.00
7g
7f
H
H

7.26
7.12
OH
1.98
OH
7.10
2.00 6.83
6.81
-222.46
-222.53
4.55
4.53 -222.59
4.52 -222.60
S-123
1.10 4.43
1.11 4.41
4.40 -222.66
3.96
2.22 3.95 -222.71
3.93 -222.72
-222.78
2.63
2.62
2.61 -222.85
2.20 2.61
2.60
2.59
1.82
1.80
6.11 1.75
1.74
5.94
1.73
2.99 1.73
3.12 -222.46
1.72
-222.53
1.71
-222.59
1.61
-222.60
1.59
-222.66
1.58
-222.71
1.56
-222.72
1.55
-222.78
1.22
-222.85
0.95
0.93
0.91
F
19
157.17
0.00
O
7g
134.65
129.17

OH
114.49
-218.68
-218.74
F
-218.80
84.80
-218.81
S-124
83.17
13
-218.87 77.37
77.06
76.74
-218.93 72.85
-218.94 67.68
O
7g
-218.99
-219.06
43.47
OH
34.42
30.26
30.07
29.39
28.95
26.35
-218.68 21.97
-218.74 21.92
-218.80
-218.81
-218.87
-218.93 8.26
-218.94
-218.99
-219.06
7.26
4.48
4.46
4.45
4.36
4.34
4.33
3.84
3.83
2.21
2.18
1.98
39.83 1.97
39.68 1.96
39.42 1.95
1.93
1.90
1.88
1.87
1.86
1.86
35.42 1.84
35.35 1.84
35.05 1.83
34.62 1.81
1.80
1.73
1.69
32.86 1.68
1.67
1.66
31.19 1.65
31.15 1.62
30.66 1.51
1.49
1.48
S-125
1.47
0.99 1.46
0.97 1.45
85.33
1.44
84.02
1.41
77.29 1.39
77.04 0.98 1.38
76.79 1.36
71.98 0.98 1.35
68.52 1.32
1.31
1.29
55.93 1.28
1.27
50.47 1.26
1.25
41.50 1.11 1.24
39.68 2.41 1.20
39.42 5.45 1.17
35.42 5.12 1.16
35.05 4.05 1.14
32.86 3.45 1.13
28.23 3.13 1.12
23.69 4.49 1.12
22.80 4.30 1.10
20.60 3.04 1.09
18.54 3.00 1.09
11.78
0.97
0.96
0.94
0.00 0.92
0.90
0.66
-0.01
0.00
-217.65
-217.72
-217.78
S-126
-217.84
-217.91
-217.97
-218.03
-217.65
-217.72
-217.78
-217.84
-217.91
-217.97
-218.03

CL-SR (O) N-Ts Synthesis Method 2

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CL-SR (O) N-Ts Synthesis Method 2

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Supporting Information

Rapid Deoxyfluorination of Alcohols with N-Tosyl-4-

1. General Information ...........................................................................................S-2

Table S1. The reaction of secondary alcohols: Screening the basesa

Entry Base Yield (%)b

Typical Experimental Procedures (Table S1, entry 1):

DBU (1.1 equiv)

Entry Sulfonimidoyl fluoride Yield (%)b 3a/alkenec

Entry Time (min) Yield (%)b

toluene (0.1 M), rt, 30 min

Entry Reagent Yield (%)b 3a/alkenec

Typical Experimental Procedures (Table S8, entry 4):

O NTs DBU (1.2 equiv)

Entry External fluoride Equivalents Yield (%)b

Typical Experimental Procedures (Table S10, entry 9):

3. Preparation of SulfoxFluor (1a) and Other

3.1.2 F-Cl Exchange for Preparing SulfoxFluor (1a)

Empirical formula C13H11ClFNO3S2

DSC Thermal Analysis of SulfoxFluor (1a)

The thermal stability of SulfoxFluor (1a) was evaluated using Differential

3.2. Preparation of N-Tosylbenzenesulfonimidoyl Fluoride (1b)

3.3. Preparation of N-Tosyl-4-nitrobenzenesulfonimidoyl Fluoride

3.4. Preparation of N-Benzoyl-4-chlorobenzenesulfonimidoyl

azole 1-oxide (1e)

4.1. 3α-Hydroxy-5β-cholan-24-ol (6b)

4.2. 6-Phenethyl-8-phenyloctane-1,6-diol (6d)

4.3. 4-(4-(3-Hydroxypropoxy)phenyl)cyclohexanol (6e)

3,14,15,16, 17-decahydro-6H-cyclopenta[a]phenanthren-17-ol (6f)

4.5. 5-(4-(3-Hydroxy-3-methylpentyl)phenoxy)pentan-1-ol (6g)

4.6. 2-Methylpentane-2,4-diol (6h)

4.7. 3-Methylbutane-1,3-diol (6i)

5. Deoxyfluorination of Alcohols 2 with SulfoxFluor

Prepared from 4-(naphthalen-2-yl)butan-2-ol (2b) (40.0 mg, 0.2 mmol),

Prepared from (R)-5-(4-(benzyloxy)- phenyl)pentan-2-ol (2d) (54.0 mg, 0.2 mmol),

Prepared from 4-(4-methoxyphenyl)butan-2-ol (2e) (36.0 mg, 0.2 mmol),

Prepared from 5-(naphthalen-2-yl)pentan-1-ol (2f) (42.8 mg, 0.2 mmol),

Prepared from 3-([1,1'-biphenyl]-4-yl)propan-1-ol (2g) (42.4 mg, 0.2 mmol),

2,3,4,6-Tetra-O-benzyl-D-glucopyranosyl fluoride (3i)

Prepared from 2,3,4,6-tetra-O-benzyl-D-glucopyranose (2i) (108.2 mg, 0.2 mmol),

Prepared from 3β-hydroxy-5α-androstan-17-one (2j) (58.0 mg, 0.2 mmol),

Prepared from (E)-5-(naphthalen-2-yl)pent-4-en-1-ol (2l) (42.4 mg, 0.2 mmol),

Prepared from 5-(naphthalen-2-yl)pent-4-yn-1-ol (2m) (42.0 mg, 0.2 mmol),

Prepared from (R)-4-(3-hydroxypyrrolidine-1-carbonyl)benzaldehyde (2o) (e.e. >

(R)-Benzyl 3-fluoropyrrolidine-1-carboxylate (3p)

Prepared from (S)-benzyl 3-hydroxypyrrolidine-1-carboxylate (2p) (e.e. 99.8%;

(2S,4S)-1-tert-Butyl 2-methyl 4-fluoropyrrolidine-1,2-dicarboxylate (3q)

Prepared from N-Boc-trans-4-hydroxy-L-proline methyl ester (2q) (49.0 mg, 0.2

Prepared from 3-(pyridin-4-yl)propan-1-ol (2r) (27.4 mg, 0.2 mmol), SulfoxFluor

(S)-Ethyl 2-fluoro-4-phenylbutanoate (3s)

Prepared from 2-(naphthalen-1-yl)ethan-1-ol (2t) (34.8 mg, 0.2 mmol),

Prepared from 2-(3,4-dimethoxyphenyl)ethanol (2u) (36.4 mg, 0.2 mmol),

Prepared from 2-(4-methylthiazol-5-yl)ethanol (2v) (28.6 mg, 0.2 mmol),

Prepared from 2-(benzofuran-3-yl)ethanol (2w) (32.4 mg, 0.2 mmol), SulfoxFluor

Prepared from 2-(4-fluorophenyl)ethanol (2x) (56.0 mg, 0.4 mmol), SulfoxFluor

6. Deoxyfluorination of Multiple Alcohols 4 with

Prepared from 4-(4-(3- hydroxypropoxy)phenyl)butan-2-ol (6a) (44.8 mg, 0.2

Prepared from 3α-hydroxy-5β-cholan-24-ol (6b) (72.4 mg, 0.2 mmol), SulfoxFluor

Prepared from 6-phenethyl- 8-phenyloctane-1,6-diol (6d) (65.2 mg, 0.2 mmol),

Prepared from 4-(4-(3-hydroxyprop- oxy)phenyl)cyclohexanol (6e) (50.0 mg, 0.2

Prepared from 5-(4-(3-hydroxy-3-methylpentyl)- phenoxy)-pentan-1-ol (6g) (56.0

Performed with 2-methylpentane-2,4-diol (6h) (23.6 mg, 0.2 mmol), SulfoxFluor

7. Gram-Scale Deoxyfluorination of Alcohol 2n with