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Supporting Information

 Wiley-VCH 2014
69451 Weinheim, Germany

A 2,6-Bis(phenylamino)pyridinato Titanium Catalyst for the


Highly Regioselective Hydroaminoalkylation of Styrenes and
1,3-Butadienes**
Jaika Drfler, Till Preu, Alexandra Schischko, Marc Schmidtmann, and Sven Doye*

anie_201403203_sm_miscellaneous_information.pdf
1. General Remarks
All reactions were performed under an inert atmosphere of nitrogen in oven-dried Schlenk tubes
(Duran glassware, 100 mL, = 30 mm) equipped with Teflon stopcocks and magnetic stirring
bars (15 4.5 mm). Complex [Ti(NMe2)4] was purchased from Sigma Aldrich (purity: 99.99 %)
and used without any further purification. Hexane was used as a mixture of isomers (hexanes).
Hexanes, diethyl ether and toluene were purified by distillation (50 cm vigreux column) from
sodium wire and degassed. Prior to use, all styrenes and amines were purified by distillation
and degassed. All other chemicals were purchased from commercial sources and were used
without further purification. The dienes, styrenes, amines, [Pd 2(dba)3], 1,3-
Bis(diphenylphosphino)propane (dppp), [Ti(NMe2)4], toluene, diethyl ether and hexanes were
stored in a nitrogen-filled glovebox (M. Braun, Unilab). Unless otherwise noted, yields refer to
isolated yields of pure compounds as gauged by thin layer chromatography (TLC), 1H and 13
C
NMR spectroscopy. The ratio of regioisomers was determined by gas chromatography prior to
flash chromatography. For thin layer chromatography, silica on TLC aluminium foils with
fluorescent indicator 254 nm from Fluka was used. The substances were detected with UV light
and/or iodine. For flash chromatography, silica gel from Fluka (particle size 0.037-0.063 mm)
was used. Prior to use, light petroleum ether (b.p. 40-60 C, PE) and ethyl acetate (EtOAc) were
distilled via Raschig columns at ambient pressure. Hexanes, methyl tert-butyl ether (MTBE) and
diethyl ether (Et2O) were distilled prior to flash chromatography. All products that have already
been reported in the literature were characterized by 1H NMR, 13
C NMR and infrared (IR)
spectroscopy and GC/MS. New compounds were additionally characterized by high resolution
mass spectrometry (HRMS). NMR spectra were recorded on the following spectrometers:
Bruker Avance DPX 300, Bruker Avance DRX 500, Bruker Avance III, 500 MHz. All 1H NMR
spectra are reported in units (ppm) relative to the signal of TMS at 0.00 ppm, relative to the
signal of CDCl3 at 7.26 ppm or relative to the signal of C6D6 at 7.16 ppm, J values are given in
13
Hz. All C NMR spectra are reported in units (ppm) relative to the central line of the triplet for
CDCl3 at 77.0 ppm or C6D6 at 128.0 ppm. Infrared spectra were recorded on a Bruker Vector 22
spectrometer or a Bruker Tensor 27 spectrometer (ATR). Mass spectra were recorded on a
Finnigan MAT 95 spectrometer (EI with an ionization potential of 70 eV or CI with iso-butane as
ionization gas). GC/MS analyses were performed on a Thermo Finnigan Focus gas
chromatograph equipped with a DSQ mass detector and Agilent DB-5 column (length: 30 m,
inner diameter: 0.32 mm, film thickness: 0.25 m, (94%-Methyl)-(5%-phenyl)-(1%-
vinyl)polysiloxan). GC analyses were performed on a Shimadzu GC-2010 plus gas
chromatograph equipped with a flame ionization detector. Elemental analyses were performed

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on a Euro EA 3000 (CHNS). Melting points were determined in a capillary with a Schropp-
Gertetechnik melting point MPM-H2 apparatus.

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2. Synthesis of Complex 10
2.1. Synthesis of Ligand N2,N6-Diphenylpyridine-2,6-diamine (8)[1]

Following the procedure of Buchwald,[1] a mixture of 2,6-dibromopyridine (15.4 g, 65 mmol),


aniline (14.5 g, 156 mmol), Pd2(dba)3 (2.38 g, 2.6 mmol), dppp (2.14 g, 5.2 mmol) and NaOtBu
(17.5 g, 182 mmol) in dry toluene (130 mL) was heated to 90 C under an atmosphere of argon
for 17 h. The reaction mixture was allowed to cool to room temperature and then diethyl ether
(100 mL) was added. After the solids were filtered off through celite, the filtrate was washed with
saturated brine (2 100 mL), dried over MgSO 4, and the volatiles were removed under reduced
pressure. The obtained brown oil was taken up in light petroleum (2 L) from which the product 8
crystallized. Filtration gave the product 8 as a light yellow solid (13 g, 50 mmol, 62 %). M.p. 102
C. 1H NMR (500 MHz, CDCl3, 25 C): = 6.34 (d, 3JH,H = 8 Hz, 2 H), 6.48 (br. s, 2 H), 7.04 (tt,
3
JH,H = 7 Hz, 4JH,H = 2 Hz, 2 H), 7.29-7.38 (m, 9 H) ppm. 13
C NMR (125 MHz, DEPT, CDCl3, 25
C): = 98.8 (CH), 120.3 (CH), 122.4 (CH), 129.1 (CH), 139.4 (CH), 140.6 (C), 155.0 (C) ppm.
IR (neat): 1/ = 3400, 3253, 3039, 1589, 1577, 1504, 1443, 1379, 1304, 1223, 1159, 1101,
1075, 1031, 972, 913, 828, 780, 749, 689 cm -1.

2.2. Synthesis of Complex Bis(dimethylamino)bis(phenyl(6-(phenylamino)pyridine-2-


yl)amino))titanium (10)

A solution of compound 8 (3.00 g, 11.5 mmol) in dry diethyl ether (35 mL) was added dropwise
to a solution of [Ti(NMe2)4] (9, 1.29 g, 5.7 mmol) in the same solvent (35 mL) at room
temperature over a period of one hour. The reaction mixture was stirred at room temperature for
1 d. After removing the solvent under reduced pressure, the pure complex 10 was obtained as
an orange solid (3.00 g, 4.6 mmol, 80 %) which was re-dissolved in dry diethyl ether. By fast
evaporating the solvent at room temperature in the glove box, it was possible to obtain orange-
red crystals of 10 suitable for X-ray crystallographic analysis. M.p. 87 C (decomposition). 1H
NMR (500 MHz, C6D6, 25 C): = 3.30 (s, 12 H), 6.07 (d, 3JH,H = 8 Hz, 2 H), 6.23 (d, 3JH,H = 8
3
Hz, 2 H), 6.80-6.85 (m, 2 H), 6.89 (t, 3JH,H = 8 Hz, 2 H), 6.97 (t, 3JH,H = 7 Hz), 7.00-7.06 (m, 8 H),
7.27 (t, 3JH,H = 8 Hz, 4 H), 7.44 (d, 3JH,H = 8 Hz, 4 H), 7.58 (br. s, 2 H) ppm. 13
C NMR (125 MHz,
DEPT, C6D6, 25 C): = 47.3 (CH3), 94.5 (CH), 95.0 (CH), 122.1 (CH), 122.7 (CH), 123.5 (CH),
123.6 (CH), 128.3 (CH), 129.4 (CH), 129.5 (CH), 140.5 (C), 140.9 (CH), 149.4 (C), 153.1 (C),
165.0 (C) ppm. IR (neat): 1/ = 3336, 3306, 3033, 2850, 2811, 2763, 1589, 1566, 1484, 1439,
1380, 1364, 1305, 1226, 1153, 1089, 1074, 1049, 1037, 996, 937, 876, 841, 801, 768, 746, 696
cm-1. Elemental analysis C38H40N8Ti (656.7): calcd. C 69.51, H 6.14, N 17.06; found C 69.41, H
6.18, N 17.07.

Complex 10: Orange-red crystals, C38H40N8Ti, Mr = 656.68, dimensions 0.320 0.100 0.030
mm3, monoclinic, space group P21/c, unit cell dimensions: a = 14.3594(12) , b = 21.4244(18)
, c = 10.9842(8) , = 90, = 97.478(2), = 90, V = 3350.5(5) 3, Z = 4, ber. = 1.302
Mg/m3, max = 27.103, radiation Mo K = 0.71073 , and -scans with Bruker KAPPA
APEX-II CCD at T = 120(2) K, 70752 reflections measured, 7385 unique [Rint = 0.0669], 5631
observed [I>2(I)], intensities were corrected for Lorentz and polarization effects, an empirical
absorption correction was applied using Bruker SAINT based on the Laue symmetry of the
reciprocal space, = 0.296 mm-1, Tmin = 0.9093, Tmax = 1.0000, structure solved by direct
methods and refined against F2 with a Full-matrix least-squares algorithm using the SHELXS-
2013 software package, 436 parameters refined, hydrogen atoms were treated using
appropriate riding models, goodness of fit 0.999 for observed reflections, final residual values R1
= 0.0367, wR2 = 0.0827 for observed reflections, largest diff. peak, hole, 0.373 and -0.412 e-3.
CCDC-988865 contains the supplementary crystallographic data for 10. These data can be
obtained free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.

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3. Synthesis of Starting Materials
3.1. General Procedure for the Synthesis of N-Methylanilines[2]
N-Methylanilines were prepared via a Boc-protection, N-methylation and finally Boc-
deprotection sequence. The procedure is exemplified by the synthesis of 4-thiomethyl-N-
methylaniline (17).

A Schlenk flask, equipped with a magnetic stirring bar, was charged with di-tert-
butyldicarbonate (16.8 g, 77 mmol) and tert-butanol (50 mL) under inert atmosphere. 4-
Thiomethylaniline (9.8 g, 70 mmol) was added slowly under vigorous stirring and the reaction
mixture was heated to 40 C for 24 h. The residual solvent was removed under reduced
pressure and the crude product was crystallized from a mixture of petrol ether and methyl tert-
butyl ether. The obtained crystals were directly used after the purity had been verified via GC.
The boc-protected aniline (12.6 g, 52.6 mmol) was placed in a Schlenk flask and diluted with
dimethylformamide (200 mL) under inert atmosphere. Sodium hydride (3.15 g, 60 % in mineral
oil, 78.9 mmol) was added slowly at 0 C and then stirred for 20 min. Methyl iodide (8.97 g, 63.2
mmol) was added via syringe and the reaction mixture was stirred over night at room
temperature. The reaction mixture was extracted with diethyl ether (2 100 mL), the ether
phases were combined and the solvent was removed under reduced pressure. The residual
crude product was dissolved in dichloromethane (50 mL) and trifluoroacetic acid (6.0 g, 52.6
mmol) was added. The reaction mixture was stirred for 48 h at 40 C and the progress of the
deprotection was monitored via GC. After complete conversion, the product was obtained by
removing all other components under reduced pressure. 4-Thiomethyl-N-methylaniline (17, 5.42
g, 35.4 mmol) was obtained in an overall yield of 50 % as a yellowish liquid.

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4-Thiomethyl-N-methylaniline (17)[3]

1
H NMR (500 MHz, CDCl3, 25 C, TMS): = 2.41 (s, 3 H), 2.83 (s, 3 H), 3.71 (br. s, 1 H), 6.55-
13
6.60 (m, 2 H), 7.22-7.26 (m, 2 H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25 C): = 19.3
(CH3), 30.7 (CH3), 113.0 (CH), 124.0 (C), 131.6 (CH), 148.2 (C) ppm. GC/MS: m/z (%) = 153
[M]+ (80), 138 (100), 94 (17).

3.2. Synthesis of (E)-1,3-Dienes


General Procedures for the Synthesis of (E)-1,3-Dienes
(E)-1,3-Dienes were prepared via two different synthetic pathways. All (E)-1,3-dienes were
prepared from ,-unsaturated aldehydes.

Synthesis of (E)-1,3-Dienes from ,-Unsaturated Aldehydes by Wittig-Olefination


(General Procedures A and B)
,-Unsaturated aldehydes were either purchased from commercial sources or prepared via a
four-step synthesis (general procedure A). The following scheme shows procedure A.[4-7]

General Procedure A exemplified by the preparation of 54: A mixture of p-methylbenzaldehyde


(8.00 g, 66.6 mmol) and malonic acid (13.8 g, 133.2 mmol) was suspended in pyridine (33 mL,
0.5 mL per mmol aldehyde). Piperidine (1 mL) was added and the mixture was heated to 100 C
until no more gas formation was observed through a gas-washing bottle. The reaction mixture
was then poured into ice-cold aqueous HCl solution (2 M, 500 mL) under continuous stirring.
The pH-value was checked and adjusted with additional aqueous HCl solution to be strong
acidic. The resulting suspension was filtered and the solid cinnamic acid was washed with
aqueous HCl (2 M) until no basic reaction of the filtrate was observed. The cinnamic acid (9.26
g, 63.4 mmol, 95 %) was obtained as a colorless solid which was dried under reduced pressure
(Some cinnamic acids were recrystallized from EtOH to enhance their purity.). The cinnamic
acid (9.26 g, 63.4 mmol) was then suspended in MeOH (126 mL, 2 mL per mmol acid) and
SOCl2 (11.3 g, 95 mmol) was added. The reaction mixture was heated to 65 C for two hours.

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Subsequently, the MeOH was removed under reduced pressure and the resulting solid was
dissolved in dry hexanes under an atmosphere of argon. The solution was cooled to 50 C and
a solution of DIBAL-H in n-hexane (1 M, 126 mL, 126.0 mmol) was added slowly. After
complete addition, the reaction mixture was stirred for 2.5 h at 50 C. Then MeOH (10 mL) and
aqueous NaHCO3 solution (50 mL) were added slowly and the mixture was allowed to reach
room temperature. The resulting slurry was carefully acidified with aqueous HCl (1 M) until all
solid was dissolved. The layers were separated and the aqueous layer was extracted with
hexanes (3 100 mL). The combined organic layers were dried with MgSO4 and the solvents
were removed under reduced pressure. The resulting crude allylic alcohol was dissolved in
hexanes (400 mL, for some products, additional EtOAc was added to dissolve the entire
material). Then manganese dioxide (90.4 g, 1040 mmol) was added and the reaction mixture
was stirred under an atmosphere of argon. The progress of the reaction was monitored by thin
layer chromatography (hexanes/EtOAc, 4:1) and after complete conversion (1-4 h, depending
on the structure of the allylic alcohol), the reaction mixture was filtered through silica gel. The
solid residue was washed with EtOAc and the solvent was removed under reduced pressure.
Finally, the crude product was purified by flash column chromatography (SiO2, hexanes/EtOAc,
4:1) to give p-methylcinnamic aldehyde (6.62 g, 45.3 mmol, 87 %) as a colorless solid.

Conversion of the ,-unsaturated aldehydes to the corresponding 1,3-dienes was achieved by


Wittig-Olefination (general procedure B). The following scheme shows procedure B.[8]

General Procedure B exemplified by the preparation of 54: At 0 C under an atmosphere of


argon, a 1.6 M solution of n-butyllithium in n-hexane (34 mL, 54.4 mmol) was added to a
suspension of methyltriphenylphosphonium bromide (19.4 g, 54.4 mmol) in dry THF (300 mL).
The mixture was stirred at 0 C for 1.5 h until all phosphonium bromide had been dissolved.
Then a solution of p-methylcinnamic aldehyde (6.62 g, 45.3 mmol) in dry THF (30 mL) was
added slowly and the mixture was allowed to warm to room temperature. After stirring at room
temperature for an additional hour, silica gel (20 g) and hexanes (300 mL) were added under
continuous stirring. The precipitated Ph3PO was filtered off and the solvents were removed from
the filtrate under reduced pressure. The crude residue was purified by flash column
chromatography (SiO2, n-hexane) to give (E)-1-(p-methylphenyl)butadiene (54, 5.28 g, 36.6
mmol, 81 %) as a colorless and highly refractive liquid. The overall yield from p-
7
methylbenzaldehyde was 55 %. Prior to use for hydroaminoalkylation experiments, the diene
was degassed and transferred to a nitrogen-filled glove box.
All yields for the synthesis of 1,3-dienes that are presented in this supporting information refer to
total yields obtained from aromatic aldehydes (Procedures A and B) or commercially available
,-unsaturated aldehydes (Procedure B).

(E)-Buta-1,3-dien-1-ylbenzene (53)[9]

General procedure B was used to synthesize 53 which was isolated as a colorless liquid (79 %).
1
H NMR (500 MHz, CDCl3, 25 C) 53: = 5.18 (d, 3JH,H = 10 Hz, 1 H), 5.34 (d, 3JH,H = 17 Hz, 1
H), 6.51 (dt, 3JH,H = 17 Hz, 3JH,H = 10 Hz, 1 H), 6.57 (d, 3JH,H = 16 Hz, 1 H), 6.80 (dd, 3JH,H = 16
Hz, 3JH,H = 11 Hz, 1 H), 7.23 (t, 3JH,H = 7 Hz, 1 H), 7.32 (t, 3JH,H = 8 Hz, 2 H), 7.41 (d, 3JH,H = 7
Hz, 2 H) ppm.

(E)-1-(Buta-1,3-dien-1-yl)-4-methylbenzene (54)[9]

General procedures A and B were used to synthesize 54 which was isolated as a colorless
liquid (55 % overall yield). 1H NMR (300 MHz, CDCl3, 25 C) 54: = 2.35 (s, 3 H), 5.16 (br. d,
3
JH,H = 10 Hz, 1 H), 5.32 (br. d, 3JH,H = 17 Hz, 1 H), 6.44-6.60 (m, 2 H), 6.70-6.84 (m, 1 H), 7.14
(d, 3JH,H = 8 Hz, 2 H), 7.32 (d, 3JH,H = 8 Hz, 2 H) ppm.

(E)-1-(Buta-1,3-dien-1-yl)-4-methoxybenzene (55)[9]

General procedure B was used to synthesize 55 which was isolated as a solid (86 %). 1H NMR
(500 MHz, CDCl3, 25 C) 55: = 3.38 (s, 3 H), 5.16 (d, 3JH,H = 10 Hz, 1 H), 5.31 (d, 3JH,H = 17
Hz, 1 H), 6.52 (d, 3JH,H = 16 Hz, 1 H), 6.55 (dt, 3JH,H = 17 Hz, 3JH,H = 11 Hz, 1 H), 6.74 (dd, 3JH,H
= 16 Hz, 3JH,H = 10 Hz, 1 H), 6.83 (d, 3JH,H = 9 Hz, 2 H), 7.27 (d, 3JH,H = 9 Hz, 2 H) ppm.

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(E)-1-(Buta-1,3-dien-1-yl)-4-chlorobenzene (56)[9]

General procedures A and B were used to synthesize 56 which was isolated as a colorless
liquid (54 % overall yield). 1H NMR (500 MHz, CDCl3, 25 C) 56: = 5.19 (d, 3JH,H = 10 Hz, 1 H),
5.34 (d, 3JH,H = 17 Hz, 1 H), 6.50 (d, 3JH,H = 16 Hz, 1 H), 6.43-6.53 (m, 1 H), 6.74 (dd, 3JH,H = 16
Hz, 3JH,H = 11 Hz, 1 H), 7.27 (d, 3JH,H = 7 Hz, 2 H), 7.31 (d, 3JH,H = 8 Hz, 2 H) ppm.

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4. Hydroaminoalkylation
4.1. General Procedure C for the Hydroaminoalkylation of Alkenes with Arylalkylamines
An oven dried Schlenk tube equipped with a Teflon stopcock and a magnetic stirring bar was
transferred into a nitrogen-filled glovebox and charged with complex 10 (66 mg, 0.1 mmol, 5
mol-% or 131 mg, 0.2 mmol, 10 mol-%) and hexanes (0.5 mL). Afterwards the amine (2.0
mmol), the alkene (3.0 mmol) and hexanes (0.5 mL) were added. After heating the mixture to
140 C for 96 h, the crude product was purified by flash chromatography (SiO 2).

4.2. Optimization of the Hydroaminoalkylation of Styrene (6) with N-Methylaniline (3)


Catalyzed by Complex 10

Entry 10 [mol-%] T [C] t [h] Yield 7b [%][a] Selectivity 7a/7b[b]


1 10 140 96 83 4:96
2 10 120 96 73 5:95
3 10 100 96 59 4:96
4 10 140 24 78 7:93
5 5 140 96 81 6:94
6 5 140 24 79 6:94
7 5 140 96 79[c] 7:93
8 5 140 96 80[d] 7:93
[a] Reaction conditions: N-methylaniline (3, 214 mg, 2.0 mmol), styrene (6, 313 mg, 3.0 mmol),
10 (131 mg, 0.2 mmol, 10 mol-% or 66 mg, 0.1 mmol, 5 mol-%), hexanes (1.0 mL), T, t. Yields
refer to the yield of the isolated linear product 7b. [b] GC analysis prior to chromatography. [c]
Toluene (1 mL) was used as solvent. [d] Styrene (1 mL) was used as solvent.

4.3. General Procedure D for the Hydroaminoalkylation of Alkenes with Dialkylamines


An oven dried Schlenk tube equipped with a Teflon stopcock and a magnetic stirring bar was
transferred into a nitrogen-filled glovebox and charged with complex 10 (131 mg, 0.2 mmol, 10
mol-%) and hexanes (0.5 mL). Afterwards the amine (2.0 mmol), the alkene (3.0 mmol) and
hexanes (0.5 mL) were added. After heating the mixture to 140 C for 96 h, the crude product
10
was transferred to a 100 mL-round-bottomed flask and the Schlenk tube was rinsed with
dichloromethane (4 10 mL). The combined solutions were concentrated under vacuum to a
total volume of 10 mL. The resulting mixture was then treated with 2 N aqueous NaOH (5 mL,
10.0 mmol) and p-toluenesulfonyl chloride (572 mg, 3.0 mmol). The resulting biphasic mixture
was stirred vigorously for 20 h before the solution was partitioned between dichloromethane (50
mL) and water (20 mL). The formed layers were separated, the aqueous one was extracted with
dichloromethane (3 10 mL) and the combined organic layers were dried with MgSO 4. After
concentration under vacuum, the product was isolated by flash chromatography (SiO 2).

4.4. General Procedure E for the Hydroaminoalkylation of 1,3-Dienes with


Arylalkylamines
The general procedure is exemplified by the reaction of (E)-1-phenylbutadiene (53) with 3: An
oven dried Schlenk tube equipped with a Teflon stopcock and a magnetic stirring bar was
transferred into a nitrogen-filled glovebox and charged with 10 (131 mg, 0.20 mmol, 10 mol-%),
(E)-1-phenylbutadiene (53, 391 mg, 3.0 mmol), N-methylaniline (3, 214 mg, 2.0 mmol) and
hexanes (1 mL). Then the tube was sealed and the resulting mixture was heated to 120 C for
48 h. After the mixture had been cooled to room temperature, dichloromethane (30 mL) was
added and the ratio of the products (not isomerized/isomerized = 61:39) was determined by GC.
To achieve a better separation of the products from remaining N-methylaniline, acetyl chloride
(4 mL, 4 mmol, 1 M in dichloromethane) and triethylamine (405 mg, 4 mmol) were added to the
reaction mixture and stirred over night. The resulting acetamides were purified and isolated by
flash column chromatography (SiO2, hexanes/Et2O, 3:1) to give two fractions. Fraction 1 (118
mg, 0.42 mmol, 21 %) contained compound 57b as major component and 57a as minor
component. Fraction 2 (104 mg, 0.37 mmol, 19 %) contained compound 57a as major
component and 57b as minor component.

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N-(3-Phenylpropyl)aniline (7b)[10]

General procedure C was used to synthesize 7b from N-methylaniline (3, 214 mg, 2.0 mmol)
and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography (PE/EtOAc,
30:1), 7b (342 mg, 1.6 mmol, 81 %, catalyst system: 5 mol-% complex 10) was isolated as a
yellow oil. Prior to chromatography, the ratio 7a/7b was determined to be 6:94. 1H NMR (300
MHz, CDCl3, 25 C, TMS): = 1.94 (quin, 3JH,H = 7 Hz, 2 H), 2.73 (t, 3JH,H = 8 Hz, 2 H), 3.14 (t,
3
JH,H = 7 Hz, 2 H), 3.59 (br. s, 1 H), 6.57 (d, 3JH,H = 8 Hz, 2 H), 6.69 (t, 3JH,H = 7 Hz, 1 H), 7.08-
13
7.24 (m, 5 H), 7.24-7.34 (m, 2 H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25 C): = 31.0
(CH2), 33.4 (CH2), 43.5 (CH2), 112.9 (CH), 117.4 (CH), 125.9 (CH), 128.4 (CH), 128.4 (CH),
129.2 (CH), 141.6 (C), 148.1 (C) ppm. IR (neat): 1/ = 3411, 3083, 3053, 3024, 2934, 2858,
1603, 1507, 1321, 1258, 748, 693 cm -1. GC/MS: m/z (%) = 221 (8) [M]+, 106 (100) [C7H8N]+, 77
(27) [C6H5]+.

4-Methyl-N-(3-phenylpropyl)aniline (24b)[11]

General procedure C was used to synthesize 24b from 4-methyl-N-methylaniline (11, 242 mg,
2.0 mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(hexane/EtOAc, 30:1), 24b (329 mg, 1.5 mmol, 73 %, catalyst system: 5 mol-% complex 10)
was isolated as a yellow oil. Prior to chromatography, the ratio 24a/24b was determined to be
5:95. 1H NMR (300 MHz, CDCl3, 25 C, TMS): = 1.86 (quin, 3JH,H = 7 Hz, 2 H), 2.16 (s, 3 H),
2.65 (t, 3JH,H = 8 Hz, 2 H), 3.05 (t, 3JH,H = 7 Hz, 2 H), 6.44 (d, 3JH,H = 8 Hz, 2 H), 6.90 (d, 3JH,H = 8
13
Hz, 2 H), 7.08-7.16 (m, 3 H), 7.17-7.26 (m, 2 H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25
C): = 20.4 (CH3), 31.1 (CH2), 33.4 (CH2), 43.8 (CH2), 113.0 (CH), 125.9 (CH), 126.5 (C),
128.4 (CH), 129.7 (CH), 141.7 (C), 146.0 (C) ppm. IR (neat): 1/ = 3408, 3025, 2922, 2860,
1618, 1521, 1317, 1254, 808, 747, 700 cm -1. GC/MS: m/z (%) = 225 (23) [M]+, 120 (100)
[C8H10N]+, 91 (26) [C7H7]+.

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3-Methyl-N-(3-phenylpropyl)aniline (25b)

General procedure C was used to synthesize 25b from 3-methyl-N-methylaniline (12, 242 mg,
2.0 mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(hexane/EtOAc, 30:1), 25b (334 mg, 1.5 mmol, 74 %, catalyst system: 5 mol-% complex 10)
was isolated as a yellow oil. Prior to chromatography, the ratio 25a/25b was determined to be
5:95. 1H NMR (300 MHz, CDCl3, 25 C, TMS): = 1.86 (quin, 3JH,H = 7 Hz, 2 H), 2.18 (s, 3 H),
2.65 (t, 3JH,H = 8 Hz, 2 H), 3.05 (t, 3JH,H = 7 Hz, 2 H), 6.25-6.36 (m, 2 H), 6.44 (d, 3JH,H = 7 Hz, 1
13
H), 6.91-7.02 (m, 1 H), 7.06-7.15 (m, 3 H), 7.17-7.27 (m, 2 H) ppm. C NMR (125 MHz, DEPT,
CDCl3, 25 C): = 21.6 (CH3), 31.0 (CH2), 33.3 (CH2), 43.4 (CH2), 109.9 (CH), 113.5 (CH),
118.1 (CH), 125.9 (CH), 128.4 (CH), 129.0 (CH), 138.9 (C), 141.6 (C), 148.3 (C) ppm. IR (neat):
1/ = 3408, 3025, 2935, 2858, 1605, 1510, 1493, 1328, 1303, 769, 695 cm -1. GC/MS: m/z (%) =
225 (29) [M]+, 120 (100) [C8H10N]+, 91 (22) [C7H7]+. HRMS (EI): calcd. (C16H19N) 225.1517;
found 225.1514.

4-Fluoro-N-(3-phenylpropyl)aniline (26b)[12]

General procedure C was used to synthesize 26b from 4-fluoro-N-methylaniline (13, 250 mg,
2.0 mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(hexane/EtOAc, 30:1), 26b (329 mg, 1.4 mmol, 72 %, catalyst system: 5 mol-% complex 10)
was isolated as a yellow oil. Prior to chromatography, the ratio 26a/26b was determined to be
6:94. 1H NMR (500 MHz, CDCl3, 25 C, TMS): = 1.86 (quin, 3JH,H = 7 Hz, 2 H), 2.65 (t, 3JH,H =
8 Hz, 2 H), 3.02 (t, 3JH,H = 7 Hz, 2 H), 6.38-6.46 (m, 2 H), 6.79 (t, 3JH,H = 9 Hz, 2 H), 7.07-7.15
(m, 3 H), 7.22 (t, 3JH,H = 8 Hz, 2 H) ppm. 13
C NMR (125 MHz, DEPT, CDCl3, 25 C): = 31.0
(CH2), 33.4 (CH2), 44.1 (CH2), 113.6 (d, 3JC,F = 7 Hz, CH), 115.6 (d, 2JC,F = 22 Hz, CH), 126.0
(CH), 128.4 (CH), 128.4 (CH), 141.5 (C), 144.6 (C), 155.8 (d, 1JC,F = 235 Hz, C) ppm. IR (neat):
1/ = 3413, 3061, 3027, 2935, 2859, 1603, 1511, 1318, 1220, 819, 748, 700 cm -1. GC/MS: m/z
(%) = 229 (19) [M]+, 124 (100) [C7H7NF]+, 91 (17) [C7H7]+.

13
4-Chloro-N-(3-phenylpropyl)aniline (27b)

General procedure C was used to synthesize 27b from 4-chloro-N-methylaniline (14, 283 mg,
2.0 mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(hexane/EtOAc, 40:1), 27b (152 mg, 0.62 mmol, 31 %, catalyst system: 5 mol-% complex 10)
was isolated as a yellow oil. Prior to chromatography, the ratio 27a/27b was determined to be
6:94. 1H NMR (500 MHz, CDCl3, 25 C, TMS): = 1.95 (quin, 3JH,H = 7 Hz, 2 H), 2.73 (t, 3JH,H =
8 Hz, 2 H), 3.11 (t, 3JH,H = 7 Hz, 2 H), 6.51 (d, 3JH,H = 9 Hz, 2 H), 7.07-7.13 (m, 2 H), 7.16-7.23
13
(m, 3 H), 7.27-7.32 (m, 2 H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25 C): = 30.7 (CH2),
33.3 (CH2), 43.8 (CH2), 114.1 (CH), 122.1 (C), 126.0 (CH), 128.4 (CH), 128.5 (CH), 129.0 (CH),
141.4 (C), 146.4 (C) ppm. IR (neat): 1/ = 3415, 3061, 3026, 2936, 2859, 1600, 1500, 1318,
1253, 1177, 815, 749, 700 cm-1. GC/MS: m/z (%) = 245 (27) [M]+, 140 (100) [C7H7NCl]+, 91 (21)
[C7H7]+. HRMS (EI): calcd. (C15H16NCl) 245.0971; found 245.0969.

3-Bromo-N-(3-phenylpropyl)aniline (28b)

General procedure C was used to synthesize 28b from 3-bromo-N-methylaniline (15, 372 mg,
2.0 mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(PE/Et2O, 10:1), 28b (134 mg, 0.46 mmol, 23 %, catalyst system: 5 mol-% complex 5) was
isolated as a yellow oil. Prior to chromatography, the ratio 28a/28b was determined to be 5:95.
1
H NMR (500 MHz, CDCl3, 25 C, TMS): = 1.95 (quin, 3JH,H = 7 Hz, 2 H), 2.74 (t, 3JH,H = 8 Hz,
2 H), 3.13 (t, 3JH,H = 7 Hz, 2 H), 3.79 (br. s, 1 H), 6.48 (dd, 3JH,H = 8 Hz, 4JH,H = 2 Hz, 1 H), 6.71
(t, 4JH,H = 2 Hz, 1 H), 6.78-6.83 (m, 1 H), 7.01 (t, 3JH,H = 8 Hz, 1 H), 7.19-7.25 (m, 3 H), 7.32 (t,
3 13
JH,H = 8 Hz, 2 H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25 C): = 31.0 (CH2), 33.3 (CH2),
43.2 (CH2), 111.5 (CH), 115.1 (CH), 119.9 (CH), 123.3 (C), 126.0 (CH), 128.3 (CH), 128.5 (CH),
130.4 (CH), 141.4 (C), 149.5 (C) ppm. IR (neat): 1/ = 3414, 3025, 2929, 2857, 1597, 1497,
1323, 1068, 984, 761, 700 cm-1. GC/MS: m/z (%) = 289 (25) [M]+, 184 (100) [C7H7NBr]+, 91 (64)
[C7H7]+. HRMS (EI): calcd. (C15H16NBr) 289.0466; found 289.0467.

14
4-Methoxy-N-(3-phenylpropyl)aniline (29b)[10]

General procedure C was used to synthesize 29b from 4-methoxy-N-methylaniline (16, 274 mg,
2.0 mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(PE/Et2O, 5:1), 29b (356 mg, 1.48 mmol, 74 %, catalyst system: 5 mol-% complex 10) was
isolated as a red oil. Prior to chromatography, the ratio 29a/29b was determined to be 5:95. 1H
NMR (500 MHz, CDCl3, 25 C, TMS): = 1.93 (quin, 3JH,H = 7 Hz, 2 H), 2.73 (t, 3JH,H = 8 Hz, 2
H), 3.10 (t, 3JH,H = 7 Hz, 2 H), 3.73 (s, 3H), 6.55 (d, 3JH,H = 9 Hz, 2 H), 6.77 (d, 3JH,H = 9 Hz, 2 H),
7.17-7.23 (m, 3 H), 7.29 (t, 3JH,H = 8 Hz, 2 H) ppm. 13
C NMR (125 MHz, DEPT, CDCl3, 25 C):
= 31.2 (CH2), 33.4 (CH2), 44.4 (CH2), 55.8 (CH3), 114.1 (CH), 114.9 (CH), 125.9 (CH), 128.4
(CH), 128.4 (CH), 141.7 (C), 142.6 (C), 152.0 (C) ppm. IR (neat): 1/ = 3397, 3026, 2934, 2831,
1603, 1513, 1309, 1236, 1037, 819, 749, 700 cm -1. GC/MS: m/z (%) = 241 (24) [M]+, 136 (100)
[C8H10NO]+, 108 (9) [C7H8O]+, 91 (27) [C7H7]+.

4-(Methylthio)-N-(3-phenylpropyl)aniline (30b)

General procedure C was used to synthesize 30b from N-methyl-4-(methylthio)aniline (17, 307
mg, 2.0 mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 30:1), 30b (237 mg, 0.92 mmol, 46 %, catalyst system: 10 mol-% complex 10) was
isolated as a yellow oil. Prior to chromatography, the ratio 30a/30b was determined to be 6:94.
1
H NMR (500 MHz, CDCl3, 25 C, TMS): = 1.94 (quin, 3JH,H = 7 Hz, 2 H), 2.40 (s, 3 H), 2.73 (t,
3
JH,H = 8 Hz, 2 H), 3.13 (t, 3JH,H = 7 Hz, 2 H), 3.77 (br. s, 1 H), 6.52 (d, 3JH,H = 9 Hz, 2 H), 7.17-
7.23 (m, 5 H), 7.30 (t, 3JH,H = 8 Hz, 2 H) ppm. 13
C NMR (125 MHz, DEPT, CDCl3, 25 C): =
19.2 (CH3), 30.9 (CH2), 33.3 (CH2), 43.5 (CH2), 113.4 (CH), 124.1 (C), 126.0 (CH), 128.4 (CH),
128.4 (CH), 131.6 (CH), 141.5 (C), 147.1 (C) ppm. IR (neat): 1/ = 3407, 3059, 3024, 2918,
2857, 1599, 1502, 1314, 1252, 1183, 967, 815, 749, 700 cm-1. GC/MS: m/z (%) = 257 (39) [M]+,
152 (100) [C8H10NS]+, 91 (21) [C7H7]+. HRMS (EI): calcd. (C16H19NS) 257.1238; found
257.1236.

15
N-(4-Phenylbutan-2-yl)aniline (31b)[10]

General procedure C was used to synthesize 31b from N-ethylaniline (18, 242 mg, 2.0 mmol)
and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography (PE/EtOAc,
10:1), 31b (148 mg, 0.66 mmol, 33 %, catalyst system: 10 mol-% complex 10) was isolated as a
yellow oil. Prior to chromatography, the ratio 31a/31b was determined to be 1:99. 1H NMR (500
MHz, CDCl3, 25 C, TMS): = 1.21 (d, 3JH,H = 6 Hz, 3 H), 1.71-1.80 (m, 1 H), 1.82-1.92 (m, 1
H), 2.72 (t, 3JH,H = 8 Hz, 2 H), 3.42 (br. s, 1 H), 3.49 (sext, 3JH,H = 6 Hz, 1 H), 6.53 (d, 3JH,H = 8
Hz, 2 H), 6.66 (t, 3JH,H = 7 Hz, 1 H), 7.10-7.22 (m, 5 H), 7.26-7.31 (m, 2 H) ppm. 13
C NMR (125
MHz, DEPT, CDCl3, 25 C): = 20.8 (CH3), 32.5 (CH2), 38.8 (CH2), 47.9 (CH), 113.1 (CH),
116.9 (CH), 125.8 (CH), 128.4 (CH), 128.4 (CH), 129.3 (CH), 142.0 (C), 147.5 (C) ppm. IR
(neat): 1/ = 3404, 3053, 3025, 2963, 2925, 2858, 1602, 1506, 1319, 1259, 748, 694 cm -1.
GC/MS: m/z (%) = 225 (9) [M]+, 120 (100) [C8H10N]+, 91 (34) [C7H7]+.

N-(1,3-Diphenylpropyl)aniline (32b)[10]

General procedure C was used to synthesize 32b from N-phenylbenzylamine (19, 367 mg, 2.0
mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 30:1), a mixture of 32b and unreacted N-phenylbenzylamine (505 mg, catalyst
system: 10 mol-% complex 10) was isolated as a yellow oil. According to 1H NMR spectroscopy,
the mixture contained 500 mg of 32b (1.74 mmol, 87 %) and 5 mg of N-phenylbenzylamine
(0.03 mmol). Prior to chromatography, the ratio 32a/32b was determined to be 5:95. 1H NMR
(500 MHz, CDCl3, 25 C, TMS, mixture of 32b and N-phenylbenzylamine) 32b: = 2.05-2.19
(m, 2 H), 2.63-2.77 (m, 2 H), 4.05 (br. s, 1 H), 4.34 (t, 3JH,H = 7 Hz, 1 H), 6.47 (d, 3JH,H = 8 Hz, 2
H), 6.63 (t, 3JH,H = 7 Hz, 1 H), 7.02-7.10 (m, 2 H), 7.13-7.24 (m, 4 H), 7.25-7.39 (m, 6 H) ppm.
13
C NMR (125 MHz, DEPT, CDCl3, 25 C, mixture of 32b and N-phenylbenzylamine) 32b: =
32.6 (CH2), 40.2 (CH2), 57.7 (CH), 113.2 (CH), 117.2 (CH), 126.0 (CH), 126.4 (CH), 127.0 (CH),
128.4 (CH), 128.4 (CH), 128.6 (CH), 129.1 (CH), 141.4 (C), 143.8 (C), 147.2 (C) ppm. IR (neat,

16
mixture of 32b and N-phenylbenzylamine): 1/ = 3413, 3083, 3056, 3025, 2921, 2856, 1602,
1505, 1317, 1258, 1180, 749, 699 cm -1. GC/MS: m/z (%) = 287 (7) [M]+, 182 (100) [C13H12N]+,
91 (34) [C7H7]+.

2-Phenethyl-1,2,3,4-tetrahydroquinoline (33b)[13]

General procedure C was used to synthesize 33b from 1,2,3,4-tetrahydroquinoline (20, 266 mg,
2.0 mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(hexane/EtOAc, 30:1), 33b (184 mg, 0.78 mmol, 39 %, catalyst system: 10 mol-% complex 10)
was isolated as a yellow oil. Prior to chromatography, the ratio 33a/33b was determined to be
1:99. 1H NMR (500 MHz, CDCl3, 25 C, TMS): = 1.56-1.66 (m, 1 H), 1.70-1.83 (m, 2 H), 1.89-
1.97 (m, 1 H), 2.61-2.79 (m, 4 H), 3.18-3.27 (m, 1 H), 6.39 (d, 3JH,H = 8 Hz, 1 H), 6.54 (t, 3JH,H =
7 Hz, 1 H), 6.89 (t, 3JH,H = 7 Hz, 2 H), 7.10-7.16 (m, 3 H), 7.19-7.26 (m, 2 H) ppm. 13
C NMR
(125 MHz, DEPT, CDCl3, 25 C): = 26.2 (CH2), 27.9 (CH2), 32.2 (CH2), 38.2 (CH2), 51.1 (CH),
114.2 (CH), 117.2 (CH), 121.4 (CH), 125.9 (CH), 126.7 (CH), 128.3 (CH), 128.5 (CH), 129.2
(CH), 141.8 (C), 144.3 (C) ppm. IR (neat): 1/ = 3405, 3024, 2924, 2849, 1606, 1495, 1310,
1275, 747, 699 cm-1. GC/MS: m/z (%) = 237 (18) [M]+, 132 (100) [C9H10N]+, 91 (13) [C7H7]+.

N-Cyclohexyl-4-methyl-N-(3-phenylpropyl)benzenesulfonamide (34b)[10]

General procedure D was used to synthesize 34b from N-cyclohexylmethylamine (21, 226 mg,
2.0 mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 30:1 PE/EtOAc, 10:1 PE/EtOAc, 5:1), 34b (479 mg, 1.29 mmol, 65 %, catalyst
system: 10 mol-% complex 10) was isolated as a brown solid. Prior to tosylation and
chromatography, the ratio 34a/34b was determined to be 4:96. 1H NMR (500 MHz, CDCl3, 25
C, TMS): = 0.87-1.04 (m, 1 H), 1.16-1.31 (m, 4 H), 1.52-1.62 (m, 3 H), 1.66-1.75 (m, 2 H),
1.98 (quin, 3JH,H = 8 Hz, 2 H), 2.41 (s, 3 H), 2.62 (t, 3JH,H = 8 Hz, 2 H), 3.08-3.17 (m, 2 H), 3.57-
3.67 (m, 1 H), 7.15-7.22 (m, 3 H), 7.23-7.31 (m, 4 H), 7.67 (d, 3JH,H = 8 Hz, 2 H) ppm. 13
C NMR
(125 MHz, DEPT, CDCl3, 25 C): = 21.5 (CH3), 25.3 (CH2), 26.1 (CH2), 31.7 (CH2), 33.3

17
(CH2), 33.3 (CH2), 43.3 (CH2), 57.9 (CH), 125.9 (CH), 126.9 (CH), 128.4 (CH), 129.5 (CH),
138.6 (C), 141.4 (C), 142.7 (C) ppm. IR (neat): 1/ = 3061, 3026, 2936, 2859, 1496, 1453, 1335,
1158, 1001, 981, 822, 661 cm-1. GC/MS: m/z (%) = 371 (5) [M]+, 216 (7) [C15H22N]+, 91 (100)
[C7H7]+.

N-(1,3-Diphenylpropyl)-N,4-dimethylbenzenesulfonamide (35b)[10]

General procedure D was used to synthesize 35b from N-benzylmethylamine (22, 242 mg, 2.0
mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 20:1 PE/EtOAc, 10:1 PE/EtOAc, 5:1), a mixture of 35b and tosylated N-
benzylmethylamine (546 mg, catalyst system: 10 mol-% complex 10) was isolated as a yellow
oil. According to 1H NMR spectroscopy, the mixture contained 501 mg of 35b (1.32 mmol, 66 %)
and 45 mg of tosylated N-methylbenzylamine (0.16 mmol). Prior to tosylation and
chromatography, the ratio 35a/35b was determined to be 1:99. 1H NMR (500 MHz, CDCl3, 25
C, TMS, mixture of 35b and tosylated N-methylbenzylamine) 35b: = 1.86-1.96 (m, 1 H), 2.16-
2.26 (m, 1 H), 2.41 (s, 3 H), 2.46-2.61 (m, 2 H), 2.65 (s, 3 H), 5.13 (t, 3JH,H = 8 Hz, 1 H), 7.08 (d,
3
JH,H = 7 Hz, 2 H), 7.17-7.38 (m, 10 H) 7.60 (d, 3JH,H = 8 Hz, 2 H) ppm. 13
C NMR (125 MHz,
DEPT, CDCl3, 25 C, mixture of 35b and tosylated N-methylbenzylamine) 35b: = 21.5 (CH3),
28.7 (CH3), 32.3 (CH2), 32.9 (CH2), 59.6 (CH), 126.1 (CH), 127.1 (CH), 127.8 (CH), 128.1 (CH),
128.3 (CH), 128.4 (CH), 128.5 (CH), 129.5 (CH), 137.2 (C), 138.0 (C), 141.2 (C), 143.0 (C)
ppm. IR (neat, mixture of 35b and tosylated N-methylbenzylamine): 1/ = 3086, 3062, 3028,
2944, 1599, 1498, 1454, 1336, 1157, 1088, 1019, 992, 872, 659 cm -1. GC/MS: m/z (%) = 379
(4) [M]+, 274 (8) [C15H16NO2S]+, 155 (19) [C7H7O2S]+, 91 (100) [C7H7]+.

N-Hexyl-4-methyl-N-(3-phenylpropyl)benzenesulfonamide (36b)[10]

General procedure D was used to synthesize 36b from N-methylhexylamine (23, 230 mg, 2.0
mmol) and styrene (6, 313 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 30:1 PE/EtOAc, 10:1 PE/EtOAc, 5:1), a mixture of 36b and tosylated N-
methylhexylamine (239 mg, catalyst system: 10 mol-% complex 10) was isolated as a yellow oil.

18
According to 1H NMR spectroscopy, the mixture contained 209 mg of 36b (0.56 mmol, 28 %)
and 30 mg of tosylated N-methylhexylamine (0.11 mmol). Prior to tosylation and
chromatography, the ratio 36a/36b was determined to be 15:85. 1H NMR (500 MHz, CDCl3, 25
C, TMS, mixture of 36b and tosylated N-methylhexylamine) 36b: = 0.87 (t, 3JH,H = 7 Hz, 3 H),
1.20-1.29 (m, 6 H), 1.42-1.51 (m, 2 H), 1.85 (quin, 3JH,H = 8 Hz, 2 H), 2.41 (s, 3 H), 2.61 (t, 3JH,H
= 8 Hz, 2 H), 3.08 (t, 3JH,H = 8 Hz, 2 H), 3.13 (t, 3JH,H = 8 Hz, 2 H), 7.14 (d, 3JH,H = 7 Hz, 2 H),
7.19 (t, 3JH,H = 7 Hz, 1 H), 7.23-7.31 (m, 4 H), 7.65 (d, 3JH,H = 8 Hz, 2 H) ppm. 13
C NMR (125
MHz, DEPT, CDCl3, 25 C, mixture of 36b and tosylated N-methylhexylamine) 36b: = 14.0
(CH3), 21.5 (CH3), 22.5 (CH2), 26.4 (CH2), 28.6 (CH2), 30.3 (CH2), 31.4 (CH2), 33.0 (CH2), 47.7
(CH2), 48.4 (CH2), 126.0 (CH), 127.1 (CH), 128.3 (CH), 128.4 (CH), 129.5 (CH), 136.9 (C),
141.3 (C), 142.9 (C) ppm. IR (neat, mixture of 36b and tosylated N-methylhexylamine): 1/ =
3027, 2929, 2858, 1600, 1495, 1454, 1340, 1158, 1091, 815, 699 cm -1. GC/MS: m/z (%) = 373
(4) [M]+, 268 (7) [C14H22NO2S]+, 155 (24) [C7H7O2S]+, 91 (100) [C7H7]+.

N-(3-(p-Tolyl)propyl)aniline (45b)[14]

General procedure C was used to synthesize 45b from N-methylaniline (3, 214 mg, 2.0 mmol)
and 4-methylstyrene (37, 355 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 30:1), 45b (333 mg, 1.48 mmol, 74 %, catalyst system: 10 mol-% complex 10) was
isolated as a yellow oil. Prior to chromatography, the ratio 45a/45b was determined to be 9:91.
1
H NMR (500 MHz, CDCl3, 25 C, TMS): = 1.92 (quin, 3JH,H = 7 Hz, 2 H), 2.32 (s, 3 H), 2.69 (t,
3
JH,H = 8 Hz, 2 H), 3.13 (t, 3JH,H = 7 Hz, 2 H), 3.68 (br. s, 1 H), 6.58 (d, 3JH,H = 8 Hz, 2 H), 6.69 (t,
3 13
JH,H = 7 Hz, 1 H), 7.06-7.12 (m, 4 H), 7.13-7.20 (m, 2 H) ppm. C NMR (125 MHz, DEPT,
CDCl3, 25 C): = 21.0 (CH3), 31.1 (CH2), 32.9 (CH2), 43.5 (CH2), 112.8 (CH), 117.3 (CH),
128.3 (CH), 129.1 (CH), 129.2 (CH), 135.4 (C), 138.5 (C), 148.2 (C) ppm. IR (neat): 1/ = 3411,
3049, 3019, 2926, 2858, 1603, 1508, 1320, 1258, 1179, 806, 749, 692 cm -1. GC/MS: m/z (%) =
225 (13) [M]+, 106 (100) [C7H8N]+, 77 (29) [C6H5]+.

19
N-(3-(2,4-Dimethylphenyl)propyl)aniline (46b)[10]

General procedure C was used to synthesize 46b from N-methylaniline (3, 214 mg, 2.0 mmol)
and 2,4-dimethylstyrene (38, 397 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 30:1), 46b (201 mg, 0.84 mmol, 42 %, catalyst system: 10 mol-% complex 10) was
isolated as a yellow oil. Prior to chromatography, the ratio 46a/46b was determined to be 33:67.
1
H NMR (300 MHz, CDCl3, 25 C, TMS): = 1.88 (quin, 3JH,H = 7 Hz, 2 H), 2.27 (s, 3 H), 2.29 (s,
3 H), 2.68 (t, 3JH,H = 8 Hz, 2 H), 3.17 (t, 3JH,H = 7 Hz, 2 H), 3.60 (br. s, 1 H), 6.59 (d, 3JH,H = 8 Hz,
2 H), 6.69 (t, 3JH,H = 7 Hz, 1 H), 6.91-6.99 (m, 2 H), 7.00-7.07 (m, 1 H), 7.03 (d, 3JH,H = 8 Hz, 1
13
H) 7.11-7.21 (m, 2 H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25 C) : = 19.2 (CH3), 20.9
(CH3), 29.8 (CH2), 30.3 (CH2), 44.1 (CH2), 113.2 (CH), 117.8 (CH), 126.6 (CH), 128.7 (CH),
129.2 (CH), 131.1 (CH), 135.5 (C), 135.7 (C), 136.6 (C), 147.8 (C) ppm. IR (neat): 1/ = 3410,
3049, 3017, 2937, 2863, 1603, 1506, 1321, 1259, 1179, 871, 819, 748, 692 cm -1. GC/MS: m/z
(%) = 239 (19) [M]+, 106 (100) [C7H8N]+, 77 (17) [C6H5]+.

N-(3-(4-(tert-Butyl)phenyl)propyl)aniline (47b)[14]

General procedure C was used to synthesize 47b from N-methylaniline (3, 214 mg, 2.0 mmol)
and 4-(tert-butyl)styrene (39, 481 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 30:1), 47b (411 mg, 1.54 mmol, 77 %, catalyst system: 10 mol-% complex 10) was
isolated as a yellow oil. Prior to chromatography, the ratio 47a/47b was determined to be 6:94.
1
H NMR (500 MHz, CDCl3, 25 C, TMS): = 1.31 (s, 9 H), 1.96 (quin, 3JH,H = 7 Hz, 2 H), 2.70 (t,
3
JH,H = 8 Hz, 2 H), 3.16 (t, 3JH,H = 7 Hz, 2 H), 3.91 (br. s, 1 H), 6.59 (d, 3JH,H = 8 Hz, 2 H), 6.70 (t,
3
JH,H = 7 Hz, 1 H), 7.10-7.19 (m, 4 H), 7.31 (d,3JH,H = 8 Hz, 2 H) ppm. 13
C NMR (125 MHz,
DEPT, CDCl3, 25 C): = 30.9 (CH2), 31.4 (CH3), 32.8 (C), 34.4 (CH2), 43.7 (CH2), 112.9 (CH),
117.4 (CH), 125.3 (CH), 128.0 (CH), 129.2 (CH), 138.5 (C), 148.1 (C), 148.8 (C) ppm. IR (neat):
1/ = 3414, 3052, 3021, 2961, 2865, 1603, 1507, 1320, 1267, 1202, 1110, 832, 748, 692 cm-1.
GC/MS: m/z (%) = 267 (8) [M]+, 106 (100) [C7H8N]+, 77 (12) [C6H5]+.

20
N-(3-(4-(Trifluoromethyl)phenyl)propyl)aniline (48b)[10]

General procedure C was used to synthesize 48b from N-methylaniline (3, 214 mg, 2.0 mmol)
and 4-(trifluoromethyl)styrene (40, 517 mg, 3.0 mmol). After purification by flash
chromatography (PE/EtOAc/Et3N, 100:2.5:1), a mixture of 48b and ligand 8 (397 mg, catalyst
system: 10 mol-% complex 10) was isolated as a yellow oil. According to 1H NMR spectroscopy,
the mixture contained 383 mg of 48b (1.37 mmol, 69 %) and 14 mg of ligand 8 (0.05 mmol).
Prior to chromatography, the ratio 48a/48b was determined to be 2:98. 1H NMR (300 MHz,
CDCl3, 25 C, TMS, mixture of 48b and 8) 48b: = 1.95 (quin, 3JH,H = 7 Hz, 2 H), 2.79 (t, 3JH,H =
8 Hz, 2 H), 3.15 (t, 3JH,H = 7 Hz, 2 H), 3.58 (br. s, 1 H), 6.57 (d, 3JH,H = 8 Hz, 2 H), 6.70 (t, 3JH,H =
7 Hz, 1 H), 7.12-7.20 (m, 2 H), 7.30 (d, 3JH,H = 8 Hz, 2 H), 7.54 (d, 3JH,H = 8 Hz, 2 H) ppm. 13
C
NMR (125 MHz, DEPT, CDCl3, 25 C, mixture of 48b and 8) 48b: = 30.8 (CH2), 33.2 (CH2),
43.2 (CH2), 112.8 (CH), 117.4 (CH), 124.3 (q, 1JC,F = 272 Hz, CF3), 125.3 (q, 3JC,F = 3.6 Hz,
CH), 128.3 (q, 2JC,F = 32 Hz, C), 128.7 (CH), 129.3 (CH), 145.8 (C), 148.1 (C) ppm. IR (neat,
mixture of 48b and 8): 1/ = 3422, 3052, 2939, 2863, 1604, 1507, 1326, 1258, 1163, 1067, 845,
750, 693 cm-1. GC/MS: m/z (%) = 279 (15) [M]+, 106 (100) [C7H8N]+, 77 (19) [C6H5]+.

N-(3-(3-(Trifluoromethyl)phenyl)propyl)aniline (49b)

General procedure C was used to synthesize 49b from N-methylaniline (3, 214 mg, 2.0 mmol)
and 3-(trifluoromethyl)styrene (41, 517 mg, 3.0 mmol). After purification by flash
chromatography (PE/EtOAc/Et3N, 100:2.5:1), 49b (351 mg, 1.26 mmol, 63 %, catalyst system:
10 mol-% complex 10) was isolated as a yellow oil. Prior to chromatography, the ratio 49a/49b
was determined to be 2:98. 1H NMR (500 MHz, CDCl3, 25 C, TMS): = 1.96 (quin, 3JH,H = 7
Hz, 2 H), 2.79 (t, 3JH,H = 8 Hz, 2 H), 3.16 (t, 3JH,H = 7 Hz, 2 H), 3.60 (br. s, 1 H), 6.58 (d, 3JH,H = 8
Hz, 2 H), 6.70 (t, 3JH,H = 7 Hz, 1 H), 7.17 (t, 3JH,H = 8 Hz, 2 H), 7.35-7.42 (m, 2 H), 7.43-7.48 (m,
13
2 H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25 C): = 31.0 (CH2), 33.2 (CH2), 43.3 (CH2),
112.8 (CH), 117.4 (CH), 122.9 (q, 3JC,F = 3.7 Hz, CH), 124.2 (q, 1JC,F = 272 Hz, CF3), 125.0 (q,
3
JC,F = 3.6 Hz, CH), 128.8 (CH), 129.3 (CH), 130.8 (q, 2JC,F = 32 Hz, C), 131.8 (CH), 142.6 (C),
21
148.2 (C) ppm. IR (neat): 1/ = 3425, 3052, 2937, 2863, 1604, 1507, 1330, 1258, 1163, 1122,
800, 750, 693 cm-1. GC/MS: m/z (%) = 279 (11) [M]+, 159 (7) [C8H6F3]+, 106 (100) [C7H8N]+, 77
(19) [C6H5]+. HRMS (EI): calcd. (C16H16NF3) 279.1235; found 279.1234.

N-(3-(4-Chlorophenyl)propyl)aniline (50b)

General procedure C was used to synthesize 50b from N-methylaniline (3, 214 mg, 2.0 mmol)
and 4-chlorostyrene (42, 416 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 40:1 PE/EtOAc, 30:1 PE/EtOAc, 10:1), a mixture of 50b and ligand 8 (358
mg, catalyst system: 10 mol-% complex 10) was isolated as a yellow oil. According to 1H NMR
spectroscopy, the mixture contained 347 mg of 50b (1.41 mmol, 71 %) and 11 mg of ligand 8
(0.04 mmol). Prior to chromatography, the ratio 50a/50b was determined to be 4:96. 1H NMR
(500 MHz, CDCl3, 25 C, TMS, mixture of 50b and 8) 50b: = 1.91 (quin, 3JH,H = 7 Hz, 2 H),
2.69 (t, 3JH,H = 8 Hz, 2 H), 3.12 (t, 3JH,H = 7 Hz, 2 H), 3.57 (br. s, 1 H), 6.57 (d, 3JH,H = 8 Hz, 2 H),
6.69 (t, 3JH,H = 7 Hz, 1 H), 7.11 (d, 3JH,H = 8 Hz, 2 H), 7.17 (t, 3JH,H = 8 Hz, 2 H), 7.21-7.27 (m, 2
13
H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25 C, mixture of 50b and 8) 50b: = 31.0 (CH2),
32.7 (CH2), 43.2 (CH2), 112.7 (CH), 117.3 (CH), 128.5 (CH), 129.2 (CH), 129.7 (CH), 131.6 (C),
140.0 (C), 148.2 (C) ppm. IR (neat, mixture of 50b and 8): 1/ = 3418, 3054, 3027, 2925, 2856,
1603, 1506, 1491, 1320, 1259, 1090, 1013, 802, 749, 693 cm-1. GC/MS: m/z (%) = 245 (16)
[M]+, 125 (9) [C7H6Cl]+, 106 (100) [C7H8N]+, 77 (23) [C6H5]+. HRMS (EI): calcd. (C15H16NCl)
245.0971; found 245.0966.

N-(3-(4-Methoxyphenyl)propyl)aniline (51b)[14]

General procedure C was used to synthesize 51b from N-methylaniline (3, 214 mg, 2.0 mmol)
and 4-methoxystyrene (43, 403 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 20:1), 51b (323 mg, 1.34 mmol, 67 %, catalyst system: 10 mol-% complex 10) was
isolated as a grey solid. Prior to chromatography, the ratio 51a/51b was determined to be 11:89.
1
H NMR (500 MHz, CDCl3, 25 C, TMS): = 1.92 (quin, 3JH,H = 7 Hz, 2 H), 2.68 (t, 3JH,H = 8 Hz,

22
2 H), 3.13 (t, 3JH,H = 7 Hz, 2 H), 3.79 (s, 3 H), 6.59 (d, 3JH,H = 8 Hz, 2 H), 6.70 (t, 3JH,H = 7 Hz, 1
H), 6.81-6.86 (m, 2 H), 7.11 (d, 3JH,H = 9 Hz, 2 H), 7.14-7.19 (m, 2 H) ppm. 13
C NMR (125 MHz,
DEPT, CDCl3, 25 C): = 31.2 (CH2), 32.4 (CH2), 43.5 (CH2), 55.3 (CH3), 112.9 (CH), 113.8
(CH), 117.4 (CH), 129.2 (CH), 129.3 (CH), 133.6 (C), 148.1 (C), 157.8 (C) ppm. IR (neat): 1/ =
3389, 3048, 3023, 2926, 2857, 1608, 1509, 1321, 1238, 1177, 769, 749, 695 cm -1. GC/MS: m/z
(%) = 241 (14) [M]+, 148 (23) [C10H12O]+, 106 (100) [C7H8N]+, 77 (21) [C6H5]+.

N-(3-(Naphthalene-2-yl)propyl)aniline (52b)

General procedure C was used to synthesize 52b from N-methylaniline (3, 214 mg, 2.0 mmol)
and 2-vinylnaphthalene (44, 463 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 20:1), 52b (334 mg, 1.28 mmol, 64 %, catalyst system: 10 mol-% complex 10) was
isolated as a bright grey oil. Prior to chromatography, the ratio 52a/52b was determined to be
7:93. 1H NMR (500 MHz, CDCl3, 25 C, TMS): = 2.04 (quin, 3JH,H = 7 Hz, 2 H), 2.90 (t, 3JH,H =
8 Hz, 2 H), 3.18 (t, 3JH,H = 7 Hz, 2 H), 3.63 (br. s, 1 H), 6.58 (d, 3JH,H = 8 Hz, 2 H), 6.69 (t, 3JH,H =
7 Hz, 1 H), 7.16 (t, 3JH,H = 8 Hz, 2 H), 7.34 (d, 3JH,H = 8 Hz, 1 H), 7.39-7.50 (m, 2 H), 7.63 (br. s,
13
1 H), 7.74-7.84 (m, 3 H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25 C): = 30.9 (CH2), 33.5
(CH2), 43.4 (CH2), 112.7 (CH), 117.2 (CH), 125.2 (CH), 126.0 (CH), 126.4 (CH), 127.2 (CH),
127.4 (CH), 127.6 (CH), 128.0 (CH), 129.2 (CH), 132.0 (C), 133.6 (C), 139.1 (C), 148.3 (C)
ppm. IR (neat): 1/ = 3451, 3406, 3049, 3023, 2928, 2855, 1636, 1602, 1506, 1319, 1249, 1178,
1103, 856, 818, 744, 692 cm-1. GC/MS: m/z (%) = 261 (16) [M]+, 141 (11) [C11H9]+, 120 (39)
[C8H10N]+, 106 (100) [C7H8N]+, 77 (19) [C6H5]+. HRMS (EI): calcd. (C19H19N) 261.1518; found
261.1520.

N-(2-Methyloctyl)aniline (5a) and N-Nonylaniline (5b)[10]

General procedure C was used to synthesize 5a and 5b from N-methylaniline (3, 214 mg, 2.0
mmol) and 1-octene (4, 337 mg, 3.0 mmol). After purification by flash chromatography
(PE/EtOAc, 30:1), a mixture of 5a and 5b (258 mg, 1.18 mmol, 59 %, catalyst system: 10 mol-%
complex 10) was isolated as a yellow oil. Prior to chromatography, the ratio 5a/5b was

23
determined to be 89:11. 1H NMR (500 MHz, CDCl3, 25 C, TMS, mixture of two regioisomers)
5a: = 0.89 (t, 3JH,H = 7 Hz, 3 H), 0.96 (d, 3JH,H = 7 Hz, 3 H), 1.12-1.22 (m, 1 H), 1.23-1.47 (m, 9
H), 1.68-1.77 (m, 1 H), 2.87 (dd, 2JH,H = 12 Hz, 3JH,H = 7 Hz, 1 H), 3.04 (dd, 2JH,H = 12 Hz, 3JH,H =
6 Hz, 1 H), 3.66 (br. s, 1 H), 6.59 (d, 3JH,H = 8 Hz, 2 H), 6.67 (t, 3JH,H = 7 Hz, 1 H), 7.13-7.19 (m,
2 H) ppm; important signals of the minor regioisomer 5b: = 1.56-1.64 (m, 1 H), 3.09 (t, 3JH,H =
13
7 Hz, 1 H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25 C, mixture of two regioisomers) 5a: =
14.1 (CH3), 18.1 (CH3), 22.7 (CH2), 26.9 (CH2), 29.6 (CH2), 31.9 (CH2), 32.9 (CH), 34.8 (CH2),
50.3 (CH2), 112.6 (CH), 116.9 (CH), 129.2 (CH), 148.6 (C) ppm; important signals of the minor
regioisomer 5b: = 27.2 (CH2), 29.3 (CH2), 29.5 (CH2), 29.5 (CH2), 44.0 (CH2), 112.7 (CH),
117.1 (CH), 148.4 (C) ppm. IR (neat, mixture of two regioisomers): 1/ = 3421, 3052, 3021,
2956, 2926, 2855, 1603, 1507, 1467, 1320, 1259, 747, 691 cm -1. GC/MS 5a: m/z (%) = 219 (13)
[M]+, 106 (100) [C7H8N]+, 77 (9) [C6H5]+; 5b: m/z (%) = 219 (10) [M]+, 106 (100) [C7H8N]+, 77 (8)
[C6H5]+.

(E)-N-Phenyl-N-(5-phenylpent-4-en-1-yl)acetamide (57a) and (E)-N-Phenyl-N-(5-


phenylpent-3-en-1-yl)acetamide (57b)

General procedure E was used to synthesize 57a and 57b. Purification by flash
chromatogtraphy (hexanes/Et2O, 3:1) gave two fractions. Fraction 1 (118 mg, 0.42 mmol, 21 %)
contained compound 57b as major component and 57a as minor component. Fraction 2 (104
mg, 0.37 mmol, 19 %) contained compound 57a as major component and 57b as minor
component.
57a: 1H NMR (500 MHz, CDCl3, 25 C): = 1.66 (quin, 3JH,H = 8 Hz, 2 H), 1.79 (s, 3 H), 2.17 (q,
3
JH,H = 7 Hz, 2 H), 3.68-3.74 (m, 2 H), 6.11 (dt, 3JH,H = 16 Hz, 3JH,H = 7 Hz, 1 H), 6.28 (d, 3JH,H =
16 Hz, 1 H), 7.10-7.17 (m, 3 H), 7.20-7.26 (m, 4 H), 7.31(t, 3JH,H = 7 Hz, 1 H), 7.38 (t, 3JH,H = 8
13
Hz, 2 H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25 C): = 22.8 (CH3), 27.4 (CH2), 30.3
(CH2), 48.7 (CH2), 125.9 (CH), 126.9 (CH), 127.8 (CH), 128.1 (CH), 128.4 (CH), 130.3 (CH),
137.6 (C), 143.1 (C), 170.2 (C) ppm. IR (neat): 1/ = 3056, 3021, 2929, 1654, 1593, 1493, 1444,
1393, 1291, 1193, 1080, 1028, 973, 914, 739, 698 cm -1. GC/MS: m/z (%) = 279 (1) [M]+, 207
(1), 148 (6), 144 (20), 138 (6), 106 (100), 91 (12), 77 (16). HRMS (EI): calcd. (C19H21NO)
279.1618; found 279.1613.

24
Isomerized product 57b: 1H NMR (500 MHz, CDCl3, 25 C): = 1.84 (s, 3 H), 2.41 (q, 3JH,H = 7
Hz, 2 H), 3.35 (d, 3JH,H = 8 Hz, 2 H), 3.77 (t, 3JH,H = 8 Hz, 2 H), 5.43-5.50 (m, 1 H), 5.61-5.71 (m,
1 H), 7.13 (d, 3JH,H = 8 Hz, 2 H), 7.15-7.19 (m, 3 H), 7.24-7.31 (m, 2 H), 7.33-7.37 (m, 1 H), 7.41
(t, 3JH,H = 8 Hz, 2 H) ppm. 13
C NMR (125 MHz, DEPT, CDCl3, 25 C): = 22.8 (CH3), 25.9
(CH2), 33.6 (CH2), 48.7 (CH2), 125.9 (CH), 126.8 (CH), 127.9 (CH), 128.2 (CH), 128.3 (CH),
128.4 (CH), 129.7 (CH), 130.5 (CH), 140.8 (C), 143.2 (C), 170.3 (C) ppm. IR (neat): 1/ = 3084,
3061, 3025, 2929, 1655, 1595, 1494, 1392, 1362, 1295, 1278, 1202, 1072, 971, 829, 771, 737,
697, 566 cm-1. GC/MS: m/z (%) = 279 (1) [M]+, 188 (1), 148 (8), 135 (20), 106 (100), 91 (10), 77
(15).

(E)-N-Phenyl-N-(5-(p-tolyl)pent-4-en-1-yl)acetamide (58a) and (E)-N-Phenyl-N-(5-(p-


tolyl)pent-3-en-1-yl)acetamide (58b)

General procedure E was used to synthesize 58a and 58b. Purification by flash
chromatography (hexanes/Et2O, 2:1) gave two fractions. Fraction 1 (66 mg, 0.23 mmol, 11 %)
contained compound 58b as major component and 58a as minor component. Fraction 2 (126
mg, 0.43 mmol, 22 %) contained compound 58a as major component and 58b as minor
compound.
58a: 1H NMR (500 MHz, CDCl3, 25 C): = 1.69 (quin, 3JH,H = 8 Hz, 2 H), 1.84 (s, 3 H), 2.20 (q,
3
JH,H = 7 Hz, 2 H), 2.31 (s, 3 H), 3.71-3.81 (m, 2 H), 6.10 (dt, 3JH,H = 16 Hz, 3JH,H = 7 Hz, 1 H),
6.29 (d, 3JH,H = 16 Hz, 1 H), 7.08 (d, 3JH,H = 8 Hz, 2 H), 7.15-7.21 (m, 4 H), 7.35 (t, 3JH,H = 7 Hz,
1 H), 7.42 (t, 3JH,H = 8 Hz, 2 H) ppm. 13
C NMR (125 MHz, DEPT, CDCl3, 25 C): = 21.1 (CH3),
22.8 (CH3), 27.5 (CH2), 30.3 (CH2), 48.7 (CH2), 125.8 (CH), 127.8 (CH), 128.1 (CH), 128.6
(CH), 129.1 (CH), 129.7 (CH), 130.1 (CH), 134.8 (C), 136.6 (C), 143.1 (C), 170.2 (C) ppm. IR
(neat): 1/ = 3016, 2927, 2871, 1658, 1594, 1501, 1444, 1394, 1293, 1202, 1085, 1031, 975,
805, 771, 700 cm-1. GC/MS: m/z (%) = 293 (1) [M]+, 158 (32), 143 (20), 106 (100), 91 (4), 77
(11). HRMS (EI): calcd. (C20H23NO) 293.1774; found 293.1764.
Isomerized product 58b: 1H NMR (500 MHz, CDCl3, 25 C): = 1.84 (s, 3 H), 2.31 (s, 3 H), 2.40
(q, 3JH,H = 7 Hz, 2 H), 3.30 (d, 3JH,H = 8 Hz, 2 H), 3.74-3.80 (m, 2 H), 5.40-5.49 (m, 1 H), 5.59-
5.68 (m, 1 H), 7.02 (d, 3JH,H = 8 Hz, 2 H), 7.07 (d, 3JH,H = 8 Hz, 2 H), 7.16 (d, 3JH,H = 7 Hz, 2 H),
7.32-7.38 (m, 1 H), 7.41 (t, 3JH,H = 8 Hz, 2 H) ppm. 13
C NMR (125 MHz, DEPT, CDCl3, 25 C):
= 21.0 (CH3), 22.9 (CH3), 25.9 (CH2), 33.1 (CH2), 48.7 (CH2), 126.0 (CH), 126.5 (CH), 127.8

25
(CH), 128.2 (CH), 129.1 (CH), 129.7 (CH), 130.7 (CH), 135.3 (C), 137.7 (C), 143.1 (C), 170.3
(C) ppm. IR (neat): 1/ = 3017, 2976, 2961, 2923, 2869, 1656, 1595, 1513, 1495, 1444, 1392,
1295, 1202, 1086, 1073, 1024, 971, 802, 772, 731, 700, 600, 568 cm-1. GC/MS: m/z (%) = 293
(1) [M]+, 188 (1), 158 (8), 135 (13), 106 (100), 77 (12).

(E)-N-(5-(4-Methoxyphenyl)pent-4-en-1-yl)-N-phenylacetamide (59a)[15] and (E)-N-(5-(4-


Methoxyphenyl)pent-3-en-1-yl)-N-phenylacetamide (59b)

General procedure E was used to synthesize 59a and 59b. Purification by flash
chromatography (hexanes/Et2O, 1:1) gave two fractions. Fraction 1 (59 mg, 0.19 mmol, 10 %)
contained compound 59b as major component and 59a as minor component. Fraction 2 (203
mg) contained compound 59a as major component, 59b as minor component and N-acetyl-N-
methylaniline. According to 1H NMR spectroscopy, the mixture contained 156 mg of 59a/59b
(0.50 mmol, 24 %) and 47 mg of N-acetyl-N-methylaniline (0.33 mmol).
59a: 1H NMR (300 MHz, CDCl3, 25 C): = 1.68 (quin, 3JH,H = 8 Hz, 2 H), 1.83 (s, 3 H), 2.19 (q,
3
JH,H = 7 Hz, 2 H), 3.75 (t, 3JH,H = 8 Hz, 2 H), 3.78 (s, 3 H), 6.01 (dt, 3JH,H = 16 Hz, 3JH,H = 7 Hz, 1
H), 6.27 (d, 3JH,H = 16 Hz, 1 H), 6.81 (d, 3JH,H = 9 Hz, 2 H), 7.14-7.25 (m, 4 H), 7.30-7.47 (m, 5
H) ppm. GC/MS: m/z (%) = 309 (4) [M]+, 174 (60), 148 (21), 106 (100), 91 (20), 77 (28).
Isomerized product 59b: 1H NMR (500 MHz, CDCl3, 25 C): = 1.83 (s, 3 H), 2.39 (q, 3JH,H = 7
Hz, 2 H), 3.28 (d, 3JH,H = 8 Hz, 2 H), 3.74-3.81 (m, 5 H), 5.40-5.46 (m, 1 H), 5.58-5.66 (m, 1 H),
6.80 (d, 3JH,H = 9 Hz, 2 H), 7.04 (d, 3JH,H = 9 Hz, 2 H), 7.16 (d, 3JH,H = 7 Hz, 2 H), 7.32-7.37 (m, 1
13
H), 7.38-7.44 (m, 2 H) ppm. C NMR (125 MHz, DEPT, CDCl3, 25 C): = 22.8 (CH3), 25.8
(CH2), 32.6 (CH2), 48.7 (CH2), 55.2 (CH3), 113.8 (CH), 126.4 (CH), 127.9 (CH), 128.1 (CH),
129.2 (CH), 129.7 (CH), 130.9 (CH), 132.8 (C), 143.1 (C), 157.8 (C), 170.3 (C) ppm. IR (neat):
1/ = 3059, 3029, 3009, 2953, 2930, 2835, 1654, 1608, 1595, 1509, 1495, 1443, 1392, 1299,
1243, 1175, 1085, 1033, 967, 846, 815, 773, 700, 567 cm -1. GC/MS: m/z (%) = 309 (1) [M]+,
174 (30), 148 (8), 121 (6), 106 (100), 91 (7), 77 (18).

26
(E)-N-(5-(4-Chlorophenyl)pent-4-en-1-yl)-N-phenylacetamide (60a)[15] and (E)-N-(5-(4-
Chlorophenyl)pent-3-en-1-yl)-N-phenylacetamide (60b)

General procedure E was used to synthesize 60a and 60b. Purification by flash
chromatography (hexanes/Et2O, 2:1) gave two fractions. Fraction 1 (90 mg, 0.29 mmol, 14 %)
contained compound 60b as major component and 60a as minor compound. Fraction 2 (151
mg) contained compound 60a as major component, 60b as minor component and N-acetyl-N-
methylaniline. According to 1H NMR spectroscopy, the mixture contained 142 mg of 60a/60b
(0.45 mmol, 23 %) and 9 mg of N-acetyl-N-methylaniline (0.06 mmol).
60a: 1H NMR (300 MHz, CDCl3, 25 C): = 1.69 (quin, 3JH,H = 8 Hz, 2 H), 1.83 (s, 3 H), 2.21 (q,
3
JH,H = 7 Hz, 2 H), 3.71-3.79 (m, 2 H), 6.14 (dt, 3JH,H = 16 Hz, 3JH,H = 7 Hz, 1 H), 6.28 (d, 3JH,H =
16 Hz, 1 H), 7.12-7.25 (m, 5 H), 7.32-7.46 (m, 4 H) ppm.
Isomerized product 60b: 1H NMR (500 MHz, CDCl3, 25 C): = 1.83 (s, 3 H), 2.38 (q, 3JH,H = 7
Hz, 2 H), 3.31 (d, 3JH,H = 7 Hz, 2 H), 3.73-3.77 (m, 2 H), 5.44-5.51 (m, 1 H), 5.57-5.64 (m, 1 H),
7.06 (d, 3JH,H = 8 Hz, 2 H), 7.15 (d, 3JH,H = 8 Hz, 2 H), 7.22 (d, 3JH,H = 8 Hz, 2 H), 7.36 (t, 3JH,H =
7 Hz, 1 H), 7.42 (t, 3JH,H = 8 Hz, 2 H) ppm. 13
C NMR (125 MHz, DEPT, CDCl3, 25 C): = 22.8
(CH3), 25.9 (CH2), 32.8 (CH2), 48.7 (CH2), 127.3 (CH), 127.9 (CH), 128.1 (CH), 128.5 (CH),
129.6 (CH), 129.7 (CH), 129.9 (CH), 131.6 (C), 139.2 (C), 143.1 (C), 170.3 (C) ppm. IR (neat):
1/ = 3061, 3014, 2965, 2913, 2859, 1654, 1595, 1492, 1443, 1392, 1362, 1196, 1157, 1089,
1015, 976, 842, 804, 770, 700, 638, 601, 559 cm -1. GC/MS: m/z (%) = 313 (1) [M]+, 188 (1), 148
(10), 135 (12), 106 (100), 77 (13).

27
5. NMR Spectra and GC-Analysis
N2,N6-Diphenylpyridine-2,6-diamine (8)[1]

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

28
Bis(dimethylamino)bis(phenyl(6-(phenylamino)pyridine-2-yl)amino))titanium (10)

1
H NMR (500 MHz, C6D6, 25 C)

13
C NMR (125 MHz, C6D6, 25 C)

29
4-Thiomethyl-N-methylaniline (17)[3]

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

30
Representative Gaschromatogram
Crude reaction mixture

7b

3
7a 8

31
N-(3-Phenylpropyl)aniline (7b)[10]

1
H NMR (300 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

32
4-Methyl-N-(3-phenylpropyl)aniline (24b)[11]

1
H NMR (300 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

33
3-Methyl-N-(3-phenylpropyl)aniline (25b)

1
H NMR (300 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

34
4-Fluoro-N-(3-phenylpropyl)aniline (26b)[12]

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

35
4-Chloro-N-(3-phenylpropyl)aniline (27b)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

36
3-Bromo-N-(3-phenylpropyl)aniline (28b)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

37
4-Methoxy-N-(3-phenylpropyl)aniline (29b)[10]

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

38
4-(Methylthio)-N-(3-phenylpropyl)aniline (30b)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

39
N-(4-Phenylbutan-2-yl)aniline (31b)[10]

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

40
N-(1,3-Diphenylpropyl)aniline (32b)[10] and N-Phenylbenzylamine (19)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

41
2-Phenethyl-1,2,3,4-tetrahydroquinoline (33b)[13]

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

42
N-Cyclohexyl-4-methyl-N-(3-phenylpropyl)benzenesulfonamide (34b)[10]

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

43
N-(1,3-Diphenylpropyl)-N,4-dimethylbenzenesulfonamide (35b)[10] and N-Benzyl-N,4-
dimethylbenzenesulfonamide

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

44
N-Hexyl-4-methyl-N-(3-phenylpropyl)benzenesulfonamide (36b)[10] and N-Hexyl-N,4-
dimethylbenzenesulfonamide

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

45
N-(3-(p-Tolyl)propyl)aniline (45b)[14]

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

46
N-(3-(2,4-Dimethylphenyl)propyl)aniline (46b)[10]

1
H NMR (300 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

47
N-(3-(4-(tert-Butyl)phenyl)propyl)aniline (47b)[14]

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

48
N-(3-(4-(Trifluoromethyl)phenyl)propyl)aniline (48b)[10] and N2,N6-Diphenylpyridine-2,6-
diamine (8)

1
H NMR (300 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

49
N-(3-(3-(Trifluoromethyl)phenyl)propyl)aniline (49b)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

50
N-(3-(4-Chlorophenyl)propyl)aniline (50b) and N2,N6-Diphenylpyridine-2,6-diamine (8)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

51
N-(3-(4-Methoxyphenyl)propyl)aniline (51b)[14]

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

52
N-(3-(Naphthalene-2-yl)propyl)aniline (52b)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

53
N-(2-Methyloctyl)aniline (5a) and N-Nonylaniline (5b)[10]

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

54
(E)-N-Phenyl-N-(5-phenylpent-4-en-1-yl)acetamide (57a)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

55
(E)-N-Phenyl-N-(5-phenylpent-3-en-1-yl)acetamide (57b)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

56
(E)-N-Phenyl-N-(5-(p-tolyl)pent-4-en-1-yl)acetamide (58a)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

57
(E)-N-Phenyl-N-(5-(p-tolyl)pent-3-en-1-yl)acetamide (58b)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

58
(E)-N-(5-(4-Methoxyphenyl)pent-4-en-1-yl)-N-phenylacetamide (59a)[15]

1
H NMR (300 MHz, CDCl3, 25 C)

59
(E)-N-(5-(4-Methoxyphenyl)pent-3-en-1-yl)-N-phenylacetamide (59b)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

60
(E)-N-(5-(4-Chlorophenyl)pent-4-en-1-yl)-N-phenylacetamide (60a)[15]

1
H NMR (300 MHz, CDCl3, 25 C)

61
(E)-N-(5-(4-Chlorophenyl)pent-3-en-1-yl)-N-phenylacetamide (60b)

1
H NMR (500 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

62
N-Phenyl-N-(5-(p-tolyl)pentyl)acetamide

1
H NMR (300 MHz, CDCl3, 25 C)

13
C NMR (125 MHz, CDCl3, 25 C)

63
6. References

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[2] D. Krein, T. Lowary, J. Org. Chem. 2002, 67, 4965-4967.
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1680.
[4] W. Szymanski, B. Wu, B. Weiner, S. de Wildeman, B. L. Feringa, D. B. Janssen, J. Org.
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[6] E. Winterfeldt, Synthesis 1975, 617-630.
[7] S. Tsuboi, N. Ishii, T. Sakai, I. Tari, M. Utaka, Bull. Chem. Soc. Jpn. 1990, 63, 1888-1893.
[8] Y. Nakao, H. Idei, K. Kanyiva, T. Hiyama, J. Am. Chem. Soc. 2009, 131, 5070-5071.
[9] D. A. Mundal, K. E. Lutz, R. J. Thomson, Org. Lett. 2009, 11, 465-468.
[10] J. Drfler, S. Doye, Angew. Chem. 2013, 125, 1851-1854; Angew. Chem. Int. Ed. 2013, 52,
1806-1809.
[11] C. Brahms, P. Tholen, W. Saak, S. Doye, Eur. J. Org. Chem. 2013, 7583-7592.
[12] Smithlike Beecham Corporation, WO 2007/38571 A2, 2007.
[13] N. Asao, L.-Y.Chen, M.-W. Chen, Q. Chen, T. Fujita, H. E. Ho, T. Jin, M. Yan, M. Bao, Y.
Yamamoto, Org. Lett. 2013, 15, 1484-1487.
[14] R. Kubiak, I. Prochnow, S. Doye, Angew. Chem. 2010, 122, 2683-2686; Angew. Chem. Int.
Ed. 2010, 49, 2626-2629.
[15] T. Preu, W. Saak, S. Doye, Chem. Eur. J. 2013, 19, 3833-3837.

64