1400 Bull. Chem. Soc. Jpn. Vol. 80, No. 7 (2007)
[N-(2,5-Dimethylpyrrolyl)methyl]oxirane (3c):
Enantioselective Incorporation of CO2
1H NMR
4:9 Hz), 3.19–3.23 (m, 1H), 3.82 (dd, 1H, J ¼ 4:4, 15.6 Hz),
3.88 (dd, 1H, J ¼ 3:9, 15.6 Hz), 6.92 (d, 4H, J ¼ 8:3 Hz), 7.07
(d, 4H, J ¼ 8:3 Hz); 13C NMR (CDCl3) ꢁ 20.7, 46.1, 50.5, 54.0,
120.8, 129.8, 130.9, 145.7; IR (KBr) 2914, 1607, 1510, 1359,
1230, 1114, 906, 868, 812 cmꢁ1. Mp 59.8–60.4 ꢂC; HRMS: calcd
for C17H19NO: (Mþ), 253.1467. Found: m=z 253.1467. HPLC
Daicel chiralpak AD-H (10% ethanol in hexane; flow = 1.0
(CDCl3) ꢁ 2.22 (s, 6H), 2.38 (dd, 1H, J ¼ 2:5, 4.9 Hz), 2.76 (t,
1H, J ¼ 4:9 Hz), 3.11–3.14 (m, 1H), 3.91 (dd, 1H, J ¼ 4:4,
15.6 Hz), 4.06 (dd, 1H, J ¼ 12:2, 15.6 Hz), 5.77 (s, 2H); 13C NMR
(CDCl3) ꢁ 12.6, 44.4, 45.2, 51.2, 105.4, 127.9; IR (neat) 3055,
1407, 1299, 1111, 757 cmꢁ1. HRMS: calcd for C9H13NO: (Mþ),
151.0997. Found: m=z 151.1008. HPLC: Daicel chiralcel OD-H
(0.5% 2-propanol in hexane; flow = 1.0 mL minꢁ1), 9.73 min (mi-
25
mL minꢁ1), 6.7 min (minor), 8.0 min (major); ½ꢂꢃD ¼ þ38:8ꢂ
25
nor), 11.0 min (major) ½ꢂꢃD ¼ þ8:63ꢂ (c ¼ 0:87 in CHCl3).
(c ¼ 0:54 in EtOH).
4-[N-(2,5-Dimethylpyrrolyl)methyl]-1,3-dioxolan-2-one (3c0):
1H NMR (CDCl3) ꢁ 2.23 (s, 6H), 4.02–4.16 (m, 3H), 4.51 (t, 1H,
J ¼ 8:3 Hz), 4.84–4.90 (m, 1H), 5.83 (s, 2H); 13C NMR (CDCl3) ꢁ
12.8, 45.2, 66.6, 75.7, 106.8, 127.6, 153.9; IR (KBr) 1800, 1400,
1170, 1083 cmꢁ1. Mp 88.3–88.6 ꢂC; HRMS: calcd for C8H13NO3:
(Mþ) 195.0895. Found: m=z 195.0902. HPLC Daicel chiralcel
OD-H (2% 2-propanol in hexane; flow = 1.0 mL minꢁ1), 14.5
4-(N,N-Ditolylaminomethyl)-1,3-dioxolan-2-one (3f0):
1H NMR (CDCl3) ꢁ 2.30 (s, 6H), 3.94 (dd, 1H, J ¼ 6:4,
15.1 Hz), 4.07 (dd, 1H, J ¼ 5:8, 15.1 Hz), 4.20 (dd, 1H, J ¼ 2:0,
8.3 Hz), 4.44 (t, 1H, J ¼ 8:3 Hz), 4.91–4.96 (m, 1H), 6.84 (d,
4H, J ¼ 8:3 Hz), 7.09 (d, 4H, J ¼ 8:3 Hz); 13C NMR (CDCl3) ꢁ
20.6, 54.5, 67.7, 74.5, 121.0, 130.1, 132.0, 145.3, 154.5; IR
(KBr) 1782, 1509, 1165, 1071, 809 cmꢁ1. Mp 147.0–148.2 ꢂC;
elemental analysis calcd (%) for C18H19NO3: C, 72.71; H, 6.44;
N, 4.71%. Found: C, 72.63; H, 6.33; N, 4.62%. HPLC Daicel
chiralpak AD-H (5% ethanol in hexane; flow = 1.0 mL minꢁ1),
25
min (minor), 16.2 min (major) ½ꢂꢃD ¼ ꢁ43:9ꢂ (c ¼ 0:04 in
DMSO).
N-2-Naphthalenyl-N-phenylaminomethyloxirane (3d):
1H NMR (CDCl3) ꢁ 2.59 (dd, 1H, J ¼ 2:9, 4.9 Hz), 2.79 (dd,
1H, J ¼ 3:9, 4.9 Hz), 3.27–3.30 (m, 1H), 3.96 (dd, 1H, J ¼ 2:0,
15.6 Hz), 4.08 (dd, 1H, J ¼ 3:4, 15.6 Hz), 7.00–7.43 (m, 9H),
7.67–7.74 (m, 3H); 13C NMR (CDCl3) ꢁ 46.0, 50.3, 54.1, 115.7,
121.4, 122.0, 122.1, 123.9, 126.2, 126.7, 127.4, 128.8, 129.25,
129.31, 134.5, 145.3, 147.8; IR (neat) 2977, 1407, 1299, 1111,
757 cmꢁ1. HRMS: calcd for C19H17NO: (Mþ), 275.1310. Found:
m=z 275.1301. HPLC Daicel chiralpak AD-H (10% ethanol in
hexane; flow = 1.0 mL minꢁ1), 7.3 min (major), 9.1 min (minor);
25
22.7 min (minor), 28.2 min (major); ½ꢂꢃD ¼ ꢁ14:3ꢂ (c ¼ 0:39
in CHCl3).
N,N-Diphenylaminomethyloxirane (3g): 1H NMR (CDCl3)
ꢁ 2.57 (dd, 1H, J ¼ 2:9, 4.9 Hz), 2.78 (t, 1H, J ¼ 4:9 Hz), 3.21–
3.25 (m, 1H), 3.87 (dd, 1H, J ¼ 4:9, 15.6 Hz), 3.96 (dd, 1H, J ¼
3:4, 15.6 Hz), 6.95–7.06 (m, 6H), 7.25–7.29 (m, 4H); 13C NMR
(CDCl3) ꢁ 46.0, 50.4, 53.9, 120.9, 121.6, 129.3, 147.8; IR (neat)
3003, 1723, 1601, 1452, 1345, 1315, 1273, 1111, 1071, 1025,
908 cmꢁ1. Mp 60.1–60.4 ꢂC; elemental analysis calcd (%) for
C15H15NO: C, 79.97; H, 6.71; N, 6.22%. Found: C, 79.87; H,
6.66; N, 6.24%. HPLC Daicel chiralpak IB (0.1% 2-propanol
in hexane; flow = 1.0 mL minꢁ1), 24.7 min (minor), 26.0 min
25
½ꢂꢃD ¼ þ34:0ꢂ (c ¼ 0:28 in EtOH).
4-(N-2-Naphthalenyl-N-phenylaminomethyl)-1,3-dioxolan-2-
one (3d0): 1H NMR (CDCl3) ꢁ 3.99–4.14 (m, 3H), 4.33–4.37 (m,
1H), 4.91–4.93 (m, 1H), 6.94–7.67 (m, 12H); 13C NMR (CDCl3) ꢁ
54.3, 67.4, 74.3, 116.0, 121.5, 121.9, 122.8, 124.3, 126.4, 126.7,
127.3, 129.2, 129.4, 129.5, 134.2, 144.7, 147.3, 154.3; IR (KBr)
1797, 1595, 1498, 1396, 1168, 1080 cmꢁ1. HRMS: calcd for
C20H17NO3: (Mþ), 319.1208. Found: m=z 319.1196. HPLC Daicel
chiralpak AD-H (10% ethanol in hexane; flow = 1.0 mL minꢁ1),
25
(major). ½ꢂꢃD ¼ þ41:4ꢂ (c ¼ 1:06 in EtOH).
4-(N,N-Diphenylaminomethyl)-1,3-dioxolan-2-one
(3g0):
1H NMR (CDCl3) ꢁ 4.02 (dd, 1H, J ¼ 6:3, 15.1 Hz), 4.13 (dd,
1H, J ¼ 5:9, 15.1 Hz), 4.19 (dd, 1H, J ¼ 6:8, 8.8 Hz), 4.46 (t,
1H, J ¼ 8:8 Hz), 4.94–5.00 (m, 1H), 6.97–7.05 (m, 6H), 7.26–
7.33 (m, 4H); 13C NMR (CDCl3) ꢁ 54.4, 67.6, 74.4, 121.2,
122.7, 129.7, 147.4, 154.2; IR (KBr) 1789, 1497, 1182, 1078,
754, 697 cmꢁ1. Mp 98.9–99.1 ꢂC; elemental analysis calcd (%)
for C16H15NO3: C, 71.36; H, 5.61; N, 5.20%. Found: C, 71.24;
H, 5.57; N, 5.15%. HPLC Daicel chiralpak IA (7% ethylacetate
in hexane; flow = 1.0 mL minꢁ1), 16.5 min (minor), 18.1 min
25
18.7 min (minor), 22.5 min (major); ½ꢂꢃD ¼ ꢁ33:7ꢂ (c ¼ 0:24 in
EtOH).
N-Carbazolylmethyloxirane (3e): 1H NMR (CDCl3) ꢁ 2.57
(dd, 1H, J ¼ 2:9, 4.9 Hz), 2.80 (t, 1H, J ¼ 4:9 Hz), 3.33–3.37
(m, 1H), 4.40 (dd, 1H, J ¼ 4:9, 15.6 Hz), 4.63 (dd, 1H, J ¼ 3:7,
15.6 Hz), 7.23–7.27 (m, 2H), 7.44–7.49 (m, 4H), 8.09 (d, 2H,
J ¼ 7:8 Hz); 13C NMR (CDCl3) ꢁ 44.6, 45.4, 50.6, 108.7, 119.3,
120.3, 123.0, 125.8, 140.6; IR (KBr) 1485, 1457, 1221, 1153,
909, 747, 721 cmꢁ1. Mp 111.8–112.6 ꢂC; elemental analysis calcd
(%) for C15H13NO: C, 80.69; H, 5.87; N, 6.27%. Found: C, 80.53;
H, 5.77; N, 6.20%. HPLC Daicel chiralpak AD-H (5% ethanol
in hexane; flow = 1.0 mL minꢁ1), 11.0 min (minor), 11.9 min
25
(major). ½ꢂꢃD ¼ ꢁ13:8ꢂ (c ¼ 1:18 in CHCl3).
This work was supported by a Grant-in-Aid for Scientific
Research on Priority Areas ‘‘Advanced Molecular Transforma-
tions of Carbon Resources’’ from the Ministry of Education,
Culture, Sports, Science and Technology, Japan.
25
(major); ½ꢂꢃD ¼ þ11:1ꢂ (c ¼ 1:02 in CHCl3).
4-(Carbazolylmethyl)-1,3-dioxolan-2-one (3e0):
1H NMR
References
(CDCl3) ꢁ 4.28 (dd, 1H, J ¼ 6:6, 8.8 Hz), 4.47 (t, 1H, J ¼
8:8 Hz), 4.60 (dd, 1H, J ¼ 5:3, 15.9 Hz), 4.65 (dd, 1H, J ¼ 5:4,
15.9 Hz), 5.16–5.22 (m, 1H), 7.26–7.52 (m, 6H), 8.10 (d, 2H, J ¼
7:8 Hz); 13C NMR (CDCl3) ꢁ 44.6, 66.9, 74.9, 108.2, 120.0, 120.6,
123.3, 126.3, 140.3, 153.9; IR (KBr) 3447, 1781, 1456, 1162,
1042, 754 cmꢁ1. Mp 189.6–191.1 ꢂC; HRMS: calcd for C16H13-
NO3: (Mþ), 267.0895. Found: m=z 267.0902. Daicel chiralpak
IA (10% ethanol in hexane; flow = 1.0 mL minꢁ1), 15.0 min
1
a) W. C. Troger, J. Chem. Educ. 1995, 72, 973. b) B.
Hileman, Chem. Eng. News 1999, 77, 37. c) M. M. Halmann,
Chemical Fixation of Carbon Dioxide-Methods for Recycling
CO2 into Useful Products, CRC Press, Boca Raton, FL, 1993.
2
H. Arakawa, M. Aresta, J. N. Armor, M. A. Barteau, E. J.
Bechmann, A. T. Bell, J. E. Bercaw, C. Creutz, E. Dinjus, D. A.
Dixon, K. Domen, D. D. DuBois, J. Eckert, E. Fujita, D. H.
Gibson, W. A. Goddard, D. W. Goodmann, J. Keller, G. J. Kubas,
H. H. Kung, J. E. Lyons, L. E. Manzer, T. J. Marks, K.
Morokuma, K. N. Nicholas, E. Periana, L. Que, J. R. Nielson,
W. M. H. Sachtler, L. D. Schmidt, A. Sen, G. A. Somorjai.
25
(major), 17.3 min (minor); ½ꢂꢃD ¼ þ7:8ꢂ (c ¼ 1:65 in CHCl3).
N,N-Ditolylaminomethyloxirane (3f): 1H NMR (CDCl3) ꢁ
2.29 (s, 6H), 2.55 (dd, 1H, J ¼ 2:4, 4.9 Hz), 2.76 (t, 1H, J ¼