Supporting Information
Synthesis of Chiral Iridium Complexes Immobilized on Amphiphilic Polymers and
their Application to Asymmetric Catalysis
Shinichi Itsuno,* Yosuke Hashimoto, Naoki Haraguchi
Department of Environmental & Life Sciences, Toyohashi University of Technology, Toyohashi
441-8580 Japan
Synthesis of 4a:
A 5 mL glass ampoule equipped with a magnetic stirring bar was charged with (R,R)-1 (76 mg,
0.20 mmol), divinylbenzene (5.3 mg, 0.04 mmol), methyl methacrylate (176 mg, 1.76 mmol),
AIBN (9.8 mg, 0.06 mmol), and DMF (0.26 g) under nitrogen. The ampoule was sealed after
three freeze-thaw cycles under liquid nitrogen. The radical copolymerization was carried out at
60 oC for 24 h. The ampoule was opened and the mixture was poured into ether and filtrated by
grass filter. The resulting polymer was washed with THF, methanol, and water and dried in
vacuo to give a white solid (0.226 g). Yield 88%; Gel phase 1H NMR (300 MHz, CDCl3, δ = 0
((CH3)4Si)): δ= 0.6-1.2 (br, CH and CH2), 1.5 (s, CH3), 3.2 (s, CH3), 6.6-8.0 ppm (br, Ar-H);
13
C NMR (100 MHz, CDCl3, TMS): 17.12, 43.58, 50.10, 59.63, 126.41, 175.48 ppm; FT-IR
(KBr): v = 2949, 1730 cm−1; Elem. Anal.: Calcd C 63.53%; H 7.40%; N 2.18%. Found: C,
66.04%; H, 7.37%; N, 2.20%.
Synthesis of 4b:
The above synthetic protocol was followed by using styrene instead of methyl methacrylate. 4b:
88% yield. Gel phase 1H NMR (300 MHz, CDCl3, δ = 0 ((CH3)4Si)): δ= 0.6-2.5 (br, CH), 6.91-7.42
(m, 14H; Ar-H); 13C NMR (100 MHz, CDCl3, TMS): 20-56, 57-75, 120-135 ppm; FT-IR (KBr): v =
3383, 3299, 1321 cm-1; Elem. Anal.: Calcd C 85.83%; H 7.20%; N 2.12%. Found: C, 85.90%; H,
7.18%; N, 2.03%.
Synthesis of 4c:
The above synthetic protocol was followed by using 4-(tert-butyl)styrene instead of methyl
methacrylate. 4c: 94% yield. 13C NMR (100 MHz, CDCl3, TMS): 25.70, 31.62, 34.35, 39.85,
68.08, 77.12, 124.23, 127.59 ppm; FT-IR (KBr): v = 2958 (C-H), 1356 cm-1 (CH3); Elem. Anal.:
Calcd C 85.77%; H 9.15%; N 1.54%. Found: C, 84.84%; H, 9.07%; N, 2.02%.
Synthesis of 4d:
The above synthetic protocol was followed by using N-isopropylacrylamide instead of methyl
methacrylate. 4d: 80% yield. Gel phase 1H NMR (300 MHz, CDCl3, δ = 0 ((CH3)4Si)):
δ=0.6-2.0 (br, CH and CH2), 1.1 (CH3), 4.0 (CH), 7.8-8.2 ppm (br, Ar-H); 13C NMR (100 MHz,
CDCl3, TMS):
22.72, 31.26, 36.18, 41.64, 128.34, 162.71, 174.19 ppm; FT-IR (KBr): v =
2972, 1159, 703 cm−1; Elem. Anal.: Calcd C 65.87%; H 8.69%; N 10.80%. Found: C, 66.03%;
H, 8.39%; N, 10.20%.
Synthesis of 4e:
The above synthetic protocol was followed by using methacrylic acid instead of methyl
methacrylate. 4e: 97% yield. Gel phase 1H NMR (300 MHz, CDCl3, δ = 0 ((CH3)4Si)): δ=
0.6-1.6 (br, CH and CH2), 2.3 (s, CH3), 6.6-8.0 ppm (br, Ar-H); 13C NMR (100 MHz, CDCl3,
TMS): 30.63, 35.60, 162.18 ppm; FT-IR (KBr): v = 2935 cm−1 (C-H), 1710 cm−1 (C=O); Elem.
Anal.: Calcd C 61.19%; H 6.66%; N 2.41%. Found: C, 62.05%; H, 6.84%; N, 2.45%.
Synthesis of 4f:
A 5 mL glass ampoule equipped with a magnetic stirring bar was charged with (R,R)-1 (76 mg,
0.20 mmol), divinylbenzene (26 mg, 0.1 mmol), sodium 4-styrenesulfonate (330 mg, 1.8 mmol),
AIBN (9.8 mg, 0.06 mmol), DMF (0.40 g), and H2O (0.15 g) under nitrogen. The ampoule was
sealed after three freeze-thaw cycles under liquid nitrogen. The radical copolymerization was
carried out at 60 oC for 24 h. The ampoule was opened and the mixture was poured into ether
and filtrated by grass filter. The resulting polymer was washed with THF, methanol, and water
and dried in vacuo to give a white solid (0.427 g). Yield 94%; Gel phase NMR measurements
both in DMSO-d6 and D2O gave no analyzable peaks. FT-IR (KBr): v = 2931, 1333 cm-1; Elem.
Anal.: Calcd C 53.43%; H 4.11%; N 1.30%. Found: C, 54.29%; H, 4.18%; N, 1.22%.
Synthesis of 4g:
The synthetic protocol given for the synthesis of 4a was followed by using 3g
(4-vinylbenzyltrimethylammonium chloride) instead of methyl methacrylate. 4g: 94% yield.
Gel phase 1H NMR (300 MHz, D2O, TMS): δ= 1.4-2.0 (br, CH and CH2), 2.9 (br, CH3), 6.4-8.0
ppm (br, Ar-H);
13
C NMR (100 MHz, D2O, TMS): 51.74 ppm; FT-IR (KBr): v = 2931 cm−1;
Elem. Anal.: Calcd C 68.64%; H 8.11%; N 6.67%. Found: C, 69.15%; H, 8.00%; N, 6.41%.
Synthesis of 4h:
The synthetic protocol given for the synthesis of 4a was followed by using 3h
(4-vinylbenzyltributylammonium chloride) instead of methyl methacrylate. 4h: 95% yield.
Elem. Anal.: Calcd C 74.23%; H 10.17%; N 4.48%. Found: C, 75.08%; H, 9.59%; N, 4.57%.
Synthesis of 4i:
The synthetic protocol given for the synthesis of 4a was followed by using 3i
(2-methacryloyloxyethyl phosphorylcholine) instead of methyl methacrylate. 4i: 85% yield. Gel
phase 1H NMR (300 MHz, CD3OD, δ = TMS): δ= 0.6-1.4 (br, CH and CH2), 2.5-4.6 (br, CH2
and CH3), 6.8-8.0 ppm (br, Ar-H); 13C NMR (100 MHz, CD3OD, TMS): 18.43, 37.80, 54.95,
60.68, 64.33, 67.56, 129.40 ppm; FT-IR (KBr): v = 2955, 1248, 1163 cm−1; Elem. Anal.: Calcd
C 52.14%; H 7.94%; N 5.07%. Found: C, 52.38%; H, 7.89%; N, 4.96%.
Synthesis of 4j:
The synthetic protocol given for the synthesis of 4a was followed by using 3j instead of methyl
methacrylate. 4j: 94% yield. Elem. Anal.: Calcd C 65.69%; H 9.15%; N 4.14%. Found: C,
65.50%; H, 9.02%; N, 4.41%.
Synthesis of 4k:
The synthetic protocol given for the synthesis of 4a was followed by using 3k instead of methyl
methacrylate. 4k: 92% yield. Elem. Anal.: Calcd C 68.06%; H 9.77%; N 3.64%. Found: C,
67.68%; H, 9.49%; N, 3.47%.
Synthesis of 4l:
The synthetic protocol given for the synthesis of 4a was followed by using 3l instead of methyl
methacrylate. 4l: 95% yield. Gel phase 1H NMR (300 MHz, CDCl3, δ = 0 ((CH3)4Si)): δ=
0.6-1.8 (br, CH2, CH), 2.8-3.3 (br, CH2), 4.3-4.8 (br, CH2), 6.8-7.2 (br, Ar-H), 6.0-7.9 ppm (br,
Ar-H);
C NMR (100 MHz, DMSO-d6, TMS): δ= 13.4, 18-20, 22-24, 56-62, 125-134 ppm;
13
FT-IR (KBr): v = 1333 cm-1; Elem. Anal.: Calcd C 70.61%; H 8.72%; N 3.40%. Found: C,
70.24%; H, 8.50%; N, 3.22%.
Synthesis of 4m:
A 30 mL round-bottomed flask equipped with a magnetic stirring bar was charged with 4f
(0.204 g), cetyltrimethylammonium chloride (1.209 g, 3.78 mmol), and water (5.0 g) under
nitrogen. The reaction mixture was stirred at 60 oC for 15 h. The mixture was filtrated by grass
filter. The resulting polymer was washed with water and dried in vacuo to give a white solid
(0.297 g). Yield 74%. Gel phase 1H NMR (300 MHz, CDCl3, δ = 0 ((CH3)4Si)): δ= 0.6-2.0 (br,
CH and CH2), 1.3 (br, CH2), 2.3 (br, CH3), 6.4-8.0 ppm (br, Ar-H); 13C NMR (100 MHz, D2O,
TMS): 13.99, 22.86, 29.46, 52.52 ppm; FT-IR (KBr): v = 2931, 1333 cm-1; Elem. Anal.: Calcd C
70.08%; H 10.05%; N 3.30%. Found: C, 70.66%; H, 9.85%; N, 3.20%.
Synthesis of 4n:
The synthetic protocol given for the synthesis of 4a was followed by using 3n instead of methyl
methacrylate. 4n: 94% yield. Gel phase 1H NMR (300 MHz, CDCl3, δ = 0 ((CH3)4Si)): δ=
1.6-2.2 (br, CH and CH2), 2.3 (br, CH3), 2.9 (br, CH3), 6.4-8.0 ppm (br, Ar-H); 13C NMR (100
MHz, D2O, TMS): 20.84, 51.74, 125.26, 129.27, 140.71 ppm; FT-IR (KBr): v = 2931, 1333,
1161 cm−1; Elem. Anal.: Calcd C 66.33%; H 7.10%; N 4.37%. Found: C, 67.13%; H, 7.10%; N,
4.24%.
Synthesis of 4o:
The synthetic protocol given for the synthesis of 4a was followed by using 3o instead of methyl
methacrylate. 4o: 94% yield. Gel phase 1H NMR (300 MHz, CDCl3, δ = 0 ((CH3)4Si)): δ= 2.6
(br, CH2), 6.8-9.0 ppm (br, Ar-H); 13C NMR (100 MHz, CDCl3, TMS): 41.09, 118.94, 128.50,
132.12 ppm; FT-IR (KBr): v = 3044, 1432 cm−1; Elem. Anal.: Calcd C 77.47%; H 5.85%; N
0.69%. Found: C, 75.96%; H, 6.15%; N, 0.88%.
Synthesis of 4p:
The synthetic protocol given for the synthesis of 4a was followed by using 3p instead of methyl
methacrylate. 4p: 70% yield. Elem. Anal.: Calcd C 68.32%; H 8.43%; N 0.61%. Found: C,
70.04%; H, 8.15%; N, 0.78%.
Synthesis of 4q:
The synthetic protocol given for the synthesis of 4a was followed by using 3q instead of methyl
methacrylate. 4q: 85% yield. Elem. Anal.: Calcd C 73.66%; H 5.49%; N 0.55%. Found: C,
72.04%; H, 5.85%; N, 0.68%.
Polymeric Ir complex formation: Polymeric chiral ligand 4l was allowed to react with
Ir[IrCl2Cp*]2.
Formation
of
the
polymeric
Ir
(III)
complex
was
confirmed
by
gel
phase
1
H-NMR
spectra.
4l
[IrCl2Cp*]2
4l-Ir complex