Supporting Information

 Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013

A Self-Supported Polymeric MacMillan Catalyst for Homogeneous

Organocatalysis and Heterogeneous Recycling

Chang An Wang, Yuan Zhang,* Jiao Yi Shi, and Wei Wang*[a]

asia_201300152_sm_miscellaneous_information.pdf
A. General information
B. Materials and experimental procedures
C. Photos of the reaction mixture
D. SEM images of Mac-ChiOSP
E. Powder X-Ray diffraction of Mac-ChiOSP
29
F. Si MAS NMR spectrum of Mac-ChiOSP
G. FT-IR spectra for the fresh and recycled catalysts
13
H. C CP/MAS NMR spectra for the fresh and recycled catalysts
I. General procedure for the asymmetric Diels-Alder reaction
J. Evaluation of the recyclability of Mac-ChiOSP (another batch)
K. NMR and HPLC data for the products

1
A. General information
All equipment was thoroughly oven-dried. Chemicals and solvents were purchased from
commercial suppliers and, if necessary, purified before use by standard techniques.
Thin-layer chromatography (TLC) plates were visualized by exposure to ultraviolet light
and/or immersion in a solution of phosphomolybdic acid in ethanol followed by heating
on a hot plate. Flash column chromatography (FCC) was carried out with silica gel
(200300 mesh). 1H and 13C liquid NMR spectra were recorded on a Bruker Avance III
400 MHz NMR spectrometer. The chemical shifts  are given in ppm (parts per million)
relative to tetramethylsilane (TMS) and the coupling constants J are given in Hz. All the
spectra were recorded in CDCl3 or DMSO-d6 as solvent at room temperature. TMS
served as the internal standard (δ = 0.00 ppm) for 1H NMR and CDCl3 as the internal
13
standard (δ = 77.0 ppm) for C NMR. HRMS data were obtained with ESI ionization
sources on a Bruker Apex II mass instrument. Enantiomeric excess (ee) values were
determined by HPLC on a Waters 1525 Delta system with Daicel chiral OJ-H, AS-H, and
AD-H columns and with i-PrOH/n-hexane as the eluent. Elemental analysis was
performed on an Elementar Analysensysteme GmbH VarioEL V3.00 elemental analyzer.
13
C CP/MAS NMR spectra were recorded with the contact time of 2 ms (ramp 100) and
29
the pulse delay of 3 s. Si MAS NMR spectra were recorded with a 4-mm
double-resonance MAS probe, a sample spinning rate of 10.0 KHz, and with π/4
single-pulse excitation of 2.0 μs and pulse delay of 30.0 s. Surface morphologies and
microstructures of the synthesized material was examined with a Hitachi S-4800
scanning electron microscope (SEM). FT-IR spectra were recorded on a Nicolet NEXUS
670 instrument. Powder X-ray diffraction (PXRD) data were collected with a Rigaku
D/MAX-2400 X-ray diffractometer operated at 40 kV and 100 mA with Cu Kα radiation
at a scan rate of 15°/min.

B. Materials and experimental procedures

Materials: DMF was dried by calcium hydride and used after distillation.
3,5-Diiodo-(L)-tyrosine dehydrate was purchased from Acros and
Rh[(cod)(CH3CN)2]BF4 was purchased from Aldrich. All the -unsaturated aldehydes
were purchased from commercial sources and used soon after purification. All anhydrous

2
reactions were carried out under dry argon by using Schlenk tube techniques. All
catalytic reactions were performed in 5 mL centrifuge tubes.

Experimental procedures:

(I) Synthesis of functional monomer 2.1

To a suspension of 3,5-diiodo-(L)-tyrosine dehydrate (4.69 g, 10.0 mmol) in
ice-cooled dry methanol (30 mL) was added dropwise thionyl chloride (2.38 g, 20.0
mmol). After the solution was stirred at room temperature overnight, the solvent was
removed under reduced pressure to give 3,5-diiodo-(L)-tyrosine methyl ester
hydrochloride as colorless solid quantatively, which was directly used in the next step
without further purification. To a solution of 33% ethanolic MeNH2 (1.53 g, 15.0 mmol)
was added 3,5-diiodo-(L)-tyrosine methyl ester hydrochloride (2.42 g, 5.0 mmol) and the
resulting solution was stirred at room temperature until the amino ester was judged to be
consumed as determined by TLC. After removal of the organic solvents under vacuum,
the residue was suspended in Et2O and then concentrated. This Et2O addition–removal
cycle was repeated several times to remove excess MeNH2. This amide hydrochloride
was treated with saturated aqueous NaHCO3 (20 mL) and stirred for 30 min. The
resulting mixture was filtered and the residue was desiccated under vacuum. To this
residue was added MeOH (25 mL), acetone (40 mL) and p-TSA (50 mg). The resulting
solution was heated to reflux for 24 h and concentrated under vacuum to afford a crude

3
product and the residue was recrystallized from MeOH to provide functional monomer 2
as colorless solid in 70% overall yield. 1H NMR (400 MHz, d6-DMSO) δ = 9.31 (s, 1H),
7.64 (s, 2H), 3.57 (d, J = 7.3 Hz, 2H), 3.34 (s, 1H), 2.87 (d, J = 13.7 Hz, 2H), 2.64 (s, 3H),
1.20 (s, 3H), 1.18 (s, 3H); 13C NMR (100 MHz, d6-DMSO) δ 172.5, 153.5, 139.7, 135.2,
86.8, 75.1, 58.9, 35.7, 27.1, 24.9, 24.7; HRMS m/z calcd for C13H16I2N2O2 (M+H):
486.9374, found: 486.9360.

(II) Synthesis of chiral bis-alkoxysilane precursor 3.2

To a mixture of Rh[(cod)(CH3CN)2]BF4 (16 mg, 0.042 mmol)，n-Bu4NBr (644 mg,
2.0 mmol) and functional monomer 2 (486 mg, 1.0 mmol) was added the distilled DMF
(3 mL) and triethylamine (832 µL, 6.0 mmol). The mixture was stirred at room
temperature for 30 min, after which triethoxysilane (728 µL, 4.0 mmol) was added
dropwise at 0 °C, and the stirring was continued at 120 °C for 2 h. The reaction mixture
was then concentrated under vacuum to remove DMF. The resulting mixture was treated
with Et2O to give a solution of 3 in Et2O, which was filtered and the filter cake was
rinsed with Et2O. The combined filtrates were concentrated under vacuum. The residue
was purified by flash column chromatography with hexane/ethyl acetate mixture (1:1, v/v)
as eluent to give the highly purified product 3 (274 mg, 49% yield) as colorless oil. 1H
NMR (400 MHz, CDCl3) δ 7.43 (d, J = 2.2 Hz, 1H), 7.15 (dd, J = 8.3, 2.3 Hz, 1H), 6.99
(d, J = 8.4 Hz, 1H), 3.85 (dq, J = 24.1, 7.0 Hz, 12H), 3.71 (t, J = 5.4 Hz, 1H), 2.98 (qd, J
= 14.3, 5.4 Hz, 2H), 2.70 (s, 3H), 1.65 (s, 1H), 1.22 (s, 3H), 1.17 (td, J = 7.0, 3.0 Hz,
13
18H), 1.09 (s, 3H); C NMR (100 MHz, CDCl3) δ 173.4, 157.8, 138.5, 133.1, 129.5,
120.8, 117.7, , 75.4, 59.4, 59.1, 58.4, 36.2, 27.0, 25.4, 25.0, 18.1, 17.9; HRMS m/z calcd
for C25H46N2O8Si2 (M+H): 559.2865, found: 559.2869.

(III) Synthesis of chiral organosilica polymer (Mac-ChiOSP).3

Water (99 mg, 5.50 mmol) and THF (1.0 mL) were added to a stirred bis-alkoxysilane
precursor 3 (512 mg, 0.92 mmol) and then the mixture was left under static condition.
After 7 days, a pale-yellow solid was formed. After abrasion, the obtained powder was
then washed with water, ethyl ether and dried under vacuum for 12 h to give
Mac-ChiOSP (165 mg).

4
C. Photos of the reaction mixture

Fig. S1a: Photos of the reaction mixture in different solvents

Fig. S1b: Addition of Et2O (from 0.0 to 2.0 mL) for catalyst precipitation

5
D. SEM images of Mac-ChiOSP

Fig. S2 SEM images of Mac-ChiOSP

E. Powder X-Ray diffraction of Mac-ChiOSP

Fig. S3 Powder X-ray diffraction pattern of Mac-ChiOSP. No intensive diffraction peaks

were observable.

6
F. 29Si MAS NMR spectrum of Mac-ChiOSP

Fig. S4 29Si MAS NMR spectrum of Mac-ChiOSP. The signals at 62, 70 and 78 ppm
are representative for the T-type organosilica species. The appearance of Qn signals (n =
24, = 92 to 108) indicates that some cleavage of SiC bonds took place during the
synthesis of Mac-ChiOSP.

7
G. FT-IR spectra for the fresh and recycled catalysts

Fig. S5 FT-IR spectra of Mac-ChiOSP as the fresh catalyst (in black) and as the recycled
catalyst after three-time catalytic reactions (in red).

8
H. 13C CP/MAS NMR spectra for the fresh and the recycled catalysts

13
Fig. S6 Solid-state C CP/MAS NMR spectra of Mac-ChiOSP as the fresh catalyst (in
black) and as the recycled catalyst after three-time catalytic reactions (in red). Each 13C
13
CP/MAS spectrum was recorded at an MAS rate of 10.0 kHz and the data of the C
NMR chemical shift were reported relative to Me4Si. Asterisks denote spinning sidebands.
After three-time use, the partial decomposition of the catalyst took place as evidenced by
the 13C CP/MAS NMR result.

9
I. General procedure for the asymmetric Diels-Alder reaction. 1
To a stirred solution of Mac-ChiOSP (0.05 mmol) in a binary mixed solvent,
CH3CN/H2O (95/5, v/v, 1.0 mL), trifluoroacetic acid (0.06 mmol) was added and the
mixture was stirred for 5 min at room temperature. -Unsaturated aldehyde (used soon
after purification, 1.0 eq, 0.25 mmol) and cyclopentadiene (5.0 eq, 1.25 mmol) were
added in sequence. The mixture was then stirred at 23 °C in open air. After the reaction,
12 mL of Et2O was added to precipitate the catalyst, and the organic layer was separated
by centrifugation and the subsequent decantation. After the evaporation of the solvent
under vacuum, the residue was purified by flash column chromatography with
hexane/ethyl acetate as eluent to give the product as oil. Ratio of endo and exo was
determined by 1H liquid NMR (400 MHz).

(1S, 2S, 3S, 4R)-3-Phenylbicyclo[2.2.1]hex-5-ene-2-carboxaldehyde and (1R, 2S, 3S,

4S)-3-phenylbicyclo[2.2.1]hex-5-ene-2-carboxaldehyde (Table 2, entry 1).

Prepared according to the general procedure with

(E)-cinnamaldehyde and cyclopentadiene. The products were collected as a colorless oil
in 94% yield after silica gel chromatography (hexane:ethyl acetate = 10:1); endo 86% ee,
exo 90% ee. The products were converted to the corresponding alcohols with NaBH4 and
the enantiomers were separated by HPLC using a Daicel chiral OJ-H column (70/30
hexane/i-PrOH); flow rate 1.0 ml/min, 230 nm; endo isomer [TR1 = 14.1 min (major),
TR2 = 7.4 min (minor)], exo isomer [TR1 = 22.1 min (major), TR2 = 17.6 min (minor)].
Spectroscopic data are in agreement with the published data.4

(1S, 2S, 3S, 4R)-3-(2-Naphtyl)-bicyclo[2.2.1]hex-5-ene-2-carboxaldehyde and (1R, 2S,

3S, 4S)-3-(2-naphtyl)-bicyclo[2.2.1]hex-5-ene-2-carboxaldehyde (Table 2, entry 2).5

Prepared according to the general procedure with

3-naphthalen-2-yl-propenal and cyclopentadiene. The products were collected as a

10
colorless oil in 71% yield after silica gel chromatography (hexane:ethyl acetate = 10:1);
endo 89% ee, exo 81% ee. The products were converted to the corresponding alcohols
with NaBH4 and the enantiomers were separated by HPLC using a Daicel chiral OJ-H
column (70/30 hexane/i-PrOH); flow rate 1.0 ml/min, 210 nm; endo isomer [TR1 = 10.6
min (major), TR2 = 7.2 min (minor)], exo isomer [TR1 = 15.7 min (major), TR2 = 9.1 min
(minor)].
1
H NMR (400 MHz, CDCl3) exo isomer: 1H NMR (400 MHz, CDCl3) δ 9.95 (d, J = 2.0
Hz, 1H), 7.84-7.29 (m, 7H), 6.36 (dd, J = 5.6, 3.2 Hz, 1H), 6.07 (dd, J = 5.6, 2.9 Hz, 1H),
3.89-3.87 (m, 1H), 3.30–3.24 (m, 2H), 2.72 (dt, J = 5.2, 1.7 Hz, 1H), 1.89-1.59 (m, 2H).
endo isomer: δ 9.64 (d, J = 2.1 Hz, 1H), 7.84-7.29 (m, 7H), 6.45 (dd, J = 5.6, 3.3 Hz, 1H),
6.20 (dd, J = 5.6, 2.8 Hz, 1H), 3.37 (s, 1H), 3.30-3.24 (m, 2H), 3.07-3.05 (m, 1H),
13
1.89-1.59 (m, 2H). C NMR (100 MHz, CDCl3) δ 203.4, 202.7, 141.1, 140.0, 139.2,
136.5, 136.3, 133.8, 133.5, 133.2, 132.1, 132.0, 128.2, 127.7, 127.6, 127.6, 127.5, 127.5,
126.8, 126.6, 126.1, 126.0, 125.9, 125.5, 125.4, 124.7, 60.7, 59.2, 48.5, 48.2, 47.6, 47.2,
45.8, 45.6, 45.5, 45.2.

(1S, 2S, 3S, 4R)-3-o-Chlorophenylbicyclo[2.2.1]hex-5-ene-2-carboxaldehyde and (1R,

2S, 3S, 4S)-3-o-chlorophenylbicyclo [2.2.1]hex-5-ene-2-carboxaldehyde (Table 2, entry
3).

Prepared according to the general procedure with

3-(o-chlorophenyl)propenal and cyclopentadiene. The products were collected as a pale
yellow oil in 83% yield after silica gel chromatography (hexane:ethyl acetate = 6:1); endo
98% ee, exo 84% ee. The Products were converted to the corresponding alcohols with
NaBH4 and the enantiomers were separated by HPLC using a Daicel chiral AD-H column
(90/10 hexane/i-PrOH); flow rate 1.0 mL/min, 214 nm; endo isomer [TR1 = 7.0 min
(major), TR2 = 5.5 min (minor)], exo isomer [TR1 = 6.6 min (major), TR2 = 6.1 min
(minor)].
1
H NMR (400 MHz, CDCl3) exo isomer: δ 9.88 (d, J = 2.2 Hz, 1H), 7.38-6.98 (m, 5H),
6.41 (dd, J = 5.6, 3.2 Hz, 1H), 5.93 (dd, J = 5.6, 2.8 Hz, 1H), 4.18-4.16 (m, 1H),
3.37-3.26 (m, 2H), 2.63 (dt, J = 8.8, 2.8 Hz, 1H), 1.79-1.55 (m, 2H). endo isomer: δ 9.55

11
(d, J = 3.6 Hz, 1H), 7.38-6.98 (m, 5H), 6.48 (dd, J = 5.6, 3.3 Hz, 2H), 6.19 (dd, J = 5.6,
2.8 Hz, 1H), 3.37-3.26 (m, 2H), 3.13 (d, J = 1.6 Hz, 1H), 2.88-2.64 (m, 1H), 1.79-1.55 (m,
13
2H). C NMR (100 MHz, CDCl3) δ 204.6, 202.4, 140.7, 139.2, 138.8, 136.4, 136.4,
135.0, 134.9, 134.2, 129.9, 129.8, 129.4, 128.0, 127.6, 127.5, 127.4, 127.1, 126.9, 126.7,
126.2, 58.5, 58.1, 48.2, 47.8, 47.4, 47.3, 46.8, 46.1, 43.2, 42.0.

(1S, 2S, 3S, 4R)-3-p-Nitrophenylbicyclo[2.2.1]hex-5-ene-2-carboxaldehyde and (1R, 2S,

3S, 4S)-3-p-nitrophenylbicyclo[2.2.1]hex-5-ene-2-carboxaldehyde (Table 2, entry 4).5

Prepared according to the general procedure with

3-(4-nitrophenyl)propenal and cyclopentadiene. The products were collected as a pale
yellow oil in 83% yield after silica gel chromatography (hexane:ethyl acetate = 6:1); endo
76% ee, exo 92% ee. The products were converted to the corresponding alcohols with
NaBH4 and the enantiomers were separated by HPLC using a Daicel chiral AD-H column
(90/10 hexane/i-PrOH); flow rate 0.5 mL/min, 254 nm; endo isomer [TR1 = 32.9 min
(major), TR2 = 31.4 min (minor)], exo isomer [TR1 = 35.5 min (major), TR2 = 39.8 min
(minor)].
1
H NMR (400 MHz, CDCl3) exo isomer: δ 9.92 (d, J = 1.6 Hz, 1H), 8.11 (d, J = 8.8 Hz,
2H), 7.29 (d, J = 8.4 Hz, 2H), 6.41 (dd, J = 5.6, 3.2 Hz, 1H), 6.05 (dd, J = 5.6, 2.8 Hz,
1H), 3.90-3.88 (m, 1H), 3.30 (s, 1H), 3.26 (s, 1H), 2.63 (d, J = 5.0 Hz, 1H), 1.62 (s, 2H).
endo isomer: δ 9.65 (d, J = 1.6 Hz, 1H), 8.16 (d, J = 8.8 Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H),
6.44 (dd, J = 5.6, 3.3 Hz, 1H), 6.21 (dd, J = 5.6, 2.8 Hz, 1H), 3.43 (s, 1H), 3.22-3.19 (m,
13
2H), 2.97-2.95 (m, 1H), 1.77 (d, J = 8.8 Hz, 1H), 1.70 (dd, J = 8.9, 1.6 Hz, 1H). C
NMR (101 MHz, CDCl3) δ 202.1, 201.5, 151.6, 150.5, 146.5, 146.3, 139.0, 136.9, 136.0,
133.9, 128.6, 128.2, 123.8, 123.3, 61.1, 59.5, 48.4, 47.9, 47.6, 47.1, 45.5, 45.4, 45.1, 44.9.

(1S, 2S, 3S, 4R)-3-p-Bromophenylbicyclo[2.2.1]hex-5-ene-2-carboxaldehyde and (1R,

2S, 3S, 4S)-3-p-bromophenylbicyclo[2.2.1]hex-5-ene-2-carboxaldehyde (Table 2, entry
5).5

12
 Prepared according to the general procedure with
3-(4-bromophenyl)propenal and cyclopentadiene. The products were collected as a pale
yellow oil in 88% yield after silica gel chromatography (hexane:ethyl acetate = 6:1); endo
90% ee, exo 88% ee. The products were converted to the corresponding alcohols with
NaBH4 and the enantiomers were separated by HPLC using a Daicel chiral OJ-H column
(70/30 hexane/i-PrOH); flow rate 1.0 mL/min, 230 nm; endo isomer [TR1 = 7.3 min
(major), TR2 = 4.4 min (minor)], exo isomer [TR1 = 9.2 min (major), TR2 = 4.9 min
(minor)].
1
H NMR (400 MHz, CDCl3) exo isomer: δ 9.89 (d, J = 2.0 Hz, 1H), 7.37 (d, J = 8.4 Hz,
3H), 7.02 (d, J = 8.4 Hz, 2H), 6.36 (dd, J = 5.6, 3.2 Hz, 1H), 6.05 (dd, J = 5.6, 2.8 Hz,
1H), 3.69-3.67 (m, 1H), 3.23 (d, J = 1.3 Hz, 1H), 3.18 (s, 1H), 2.54 (dd, J = 3.6, 1.6 Hz,
1H), 1.76-1.56 (m, 2H). endo isomer: δ 9.59 (d, J = 2.0 Hz, 1H), 7.43 (d, J = 8.4 Hz, 2H),
7.15 (d, J = 8.4 Hz, 2H), 6.42 (dd, J = 5.6, 3.2 Hz, 1H), 6.17 (dd, J = 5.6, 2.8 Hz, 1H),
13
3.35 (s, 1H), 3.09-3.03 (m, 2H), 2.92–2.90 (m, 1H), 1.76-1.56 (m, 2H). C NMR (101
MHz, CDCl3) δ 203.0, 202.3, 142.6, 141.6, 139.1, 136.5, 136.2, 133.7, 131.6, 131.1,
129.6, 129.1, 120.1, 120.0, 60.9, 59.5, 48.3, 48.1, 47.5, 47.0, 45.4, 45.1, 45.0, 44.8.

(1S, 2S, 3S, 4R)-3-o-Methoxyphenylbicyclo[2.2.1]hex-5-ene-2-carboxaldehyde and (1R,

2S, 3S, 4S)-3-o-methoxyphenylbicyclo [2.2.1]hex-5-ene-2-carboxaldehyde (Table 2,
entry 6).6

Prepared according to the general procedure with

3-(4-methoxyphenyl)propenal, and cyclopentadiene. The products were collected as a
pale yellow oil in 44% yield after silica gel chromatography (hexane:ethyl acetate = 10:1);
endo 88% ee, exo 92% ee. The products were converted to the corresponding alcohols
with NaBH4 and the enantiomers were separated by HPLC using a Daicel chiral AS-H
column (95/5 hexane/i-PrOH); flow rate 1.0 mL/min, 214 nm; endo isomer [TR1 = 18.7
min (major), TR2 = 33.1 min (minor)], exo isomer [TR1 = 20.7 min (major), TR2 = 31.1

13
min (minor)].
1
H NMR (400 MHz, CDCl3) exo isomer: δ 9.92 (d, J = 2.1 Hz, 1H), 7.08 (d, J = 8.6 Hz,
2H), 6.80 (d, J = 8.8 Hz, 2H), 6.35 (dd, J = 5.6, 3.2 Hz, 1H), 6.08 (dd, J = 5.6, 2.8 Hz,
1H), 3.78 (s, 3H), 3.68–3.65 (m, 1H), 3.22 (d, J = 0.8 Hz, 1H), 3.18 (s, 1H), 2.54 (dt J =
5.1, 1.8 Hz, 1H), 1.81-1.56 (m, 2H). endo isomer: δ 9.59 (d, J = 2.3 Hz, 1H), 7.20 (d, J =
8.5 Hz, 2H), 6.85 (d, J = 8.8 Hz, 2H), 6.42 (dd, J = 5.6, 3.2 Hz, 1H), 6.17 (dd, J = 5.6, 2.7
Hz, 1H), 3.80 (s, 3H), 3.33 (s, 1H), 3.08 (s, 1H), 3.04 (d, J = 2.2 Hz, 1H), 2.96-2.93 (m,
1H), 1.81-1.56 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 203.7, 202.9, 158.1, 158.0, 139.2,
136.5, 136.2, 135.5, 134.6, 133.7, 128.8, 128.3, 114.0, 113.5, 60.9, 59.7, 55.3, 55.2, 48.6,
48.5, 47.6, 47.0, 45.5, 45.1, 45.0, 44.7.

References:
1. K. A. Ahrendt, C. J. Borths, D. W. C. MacMillan, J. Am. Chem. Soc. 2000, 122,
4243.
2. H. Takeda, Y. Goto, Y. Maegawa, T. Ohsuna, T. Tani, K. Matsumoto, T.
Shimadabc, S. Inagaki, Chem. Commun. 2009, 6032.
3. a) C. J. Brinker, Y. Lu, A. Sellinger, H. Fan, Adv. Mater. 1999, 11, 579; b) D. Grosso,
F. Cagnol, G. J. d. A. A. Soler-Illia, E. L. Crepaldi, H. Amenitsch, A.
Brunet-Bruneau, A. Bourgeois, C. Sanchez, Adv. Funct. Mater. 2004, 14, 309; c) J.
Fan, S. W. Boettcher, G. D. Stucky, Chem. Mater. 2006, 18, 6391; d) S. W.
Boettcher, J. Fan, C.-K. Tsung, Q. Shi, G. D. Stucky, Acc. Chem. Res. 2007, 40, 784.
4. K. Ishihara, H. Kurihara, M. Matsumoto, H. Yamamoto, J. Am. Chem. Soc. 1998,
120, 6920.
5. H. Gotoh, Y. Hayashi, Org. Lett. 2007, 9, 2859.
6. H. He, B.-J. Pei, H.-H. Chou, T. Tian, W.-H. Chan, A. M. Lee, Org. Lett. 2008, 10,
2421.

Note: The substrate scope of the Diels-Alder reaction catalyzed by

Mac-ChiOSP might be extended to the ,–unsaturated aliphatic aldehydes
as well. However, due to the inconvenience (chiral GC needed) in
determining the ee values of the corresponding products, further attempt
towards this issue has not been conducted yet.

14
J. Evaluation of the recyclability of Mac-ChiOSP (another batch)

Table S1. Evaluation of the recyclability of Mac-ChiOSP.[a, b]

Entry Recycle Time (h) Yield endo:exo[d] endo exo

Run (%)[c] ee(%)[e] ee(%)[e]
1 fresh 24 81 1:1.1 88 90
2 1st 30 84 1:1.1 90 88
3 2nd 36 66 1:1.1 80 86
4 3rd 36 46 1:1.1 84 82
5 4th 60 42 1:1.1 80 81

[a] Another synthetic batch of Mac-ChiOSP was applied. [b] The reaction was performed
with 0.05 mmol of Mac-ChiOSP, 0.06 mmol of TFA, 0.25 mmol of (E)-cinnamadehyde,
and 1.25 mmol of cyclopentadiene at rt in 1.0 mL of CH3CN/H2O (95/5, v/v). [c] Isolated
yield. [d] Determined by 1H liquid NMR. [e] The ee values were determined by HPLC
with a Daicel chiral OJ-H column after converting the product to the corresponding
alcohol with NaBH4.

Note: The high chemical purity of the endo and exo products has been
confirmed by the 1H and 13C NMR spectra (see below), which ensures the
accuracy of each isolated yield. Each endo:exo ratio has also been
determined by the corresponding 1H NMR spectrum. The ee values were
determined by chiral HPLC after, however, converting the aldehyde
products to the corresponding alcohols with NaBH4. Thus, some of the
HPLC data (see below) include additional information from unidentified
impurities. The existence of these impurities does not affect the
determination of the ee values of the desired products.

15
K. NMR and HPLC data for the products

16
17
18
19
20
21
22
HPLC data

Retention Time Area Relative Area Height

(minute) (microvolt*sec.) (%) (microvolt)
1 7.388 297074 3.59 24510
2 14.138 4152636 50.18 122814
3 17.599 175084 2.12 6103
4 22.106 3651272 44.12 45932

23
 Retention Time Area Relative Area Height
(minute) (microvolt*sec.) (%) (microvolt)
1 7.229 2343704 2.43 193405
2 9.054 5122787 5.30 284631
3 10.560 40663514 42.08 1842777
4 15.694 48493641 50.19 1070330

24
 Retention Time Area Relative Area Height
(minute) (microvolt*sec.) (%) (microvolt)
1 5.464 243354 0.70 21622
2 6.121 1130774 3.27 83536
3 6.563 13265110 38.32 1147480
4 7.008 19979078 57.71 1682915

25
 Retention Time Area Relative Area Height
(minute) (microvolt*sec.) (%) (microvolt)
1 31.395 8034641 6.44 189466
2 32.936 57258422 45.87 1242331
3 35.480 57142672 45.77 978729
4 39.764 2403512 1.93 33710

26
 Retention Time Area Relative Area Height
(minute) (microvolt*sec.) (%) (microvolt)
1 4.423 1993481 2.78 239593
2 4.920 2202887 3.07 282431
3 7.318 32648287 45.47 2244651
4 9.240 34954566 48.68 1634999

27
 Retention Time Area Relative Area Height
(minute) (microvolt*sec.) (%) (microvolt)
1 18.666 10315268 52.01 322752
2 20.696 8477555 42.74 198255
3 31.099 369633 1.86 7239
4 33.137 670567 3.38 12506

28