I. Sato et al. / Tetrahedron: Asymmetry 18 (2007) 2638–2642
2641
3057, 1638, 1601, 1125, 1038, 990, 928, 820, 747 cmꢁ1
HPLC conditions: Daicel Chiralpak AS-H; eluent: 4% 2-
propanol in hexane, flow rate, 0.7 mL/min, rt, retention
time (min): 17.0 (R)-isomer, 20.3 (S)-isomer.
.
5.18 (1H, br s), 7.2–7.3 (2H, m), 7.4–7.45 (2H, m); 13C
NMR (75 MHz, CDCl3) ppm 17.9, 77.3, 111.8, 121.4,
128.1, 131.4, 140.9, 146.4; FT-IR (neat) m 3370, 2920,
2855, 1651, 1485, 1071, 1011, 907 cmꢁ1; HRMS (ESI) calcd
for C10H10OBr ([MꢁH]ꢁ) 226.9895, found 226.9888.
HPLC conditions: Daicel Chiralpak AS-H; eluent: 1%
ethanol in hexane, flow rate, 1.0 mL/min, rt, retention time
(min): 14.8 (R)-isomer, 16.9 (S)-isomer.
4.1.7. (R)-5-Phenylpent-1-en-3-ol 2g.21 Yield 50%. 80%
21
ee. Colorless oil; ½aꢀD ¼ ꢁ5:8 (c 1.3, CHCl3); 1H NMR
(300 MHz, CDCl3) d 1.55 (1H, br s), 1.8–1.9 (2H, m),
2.6–2.8 (2H, m), 4.13 (1H, br d, J = 5.9 Hz), 5.14 (1H,
ddd, J = 10.3, 1.4, 1.4 Hz), 5.25 (1H, ddd, J = 16.9, 1.4,
1.4 Hz), 5.91 (1H, ddd, J = 16.9, 10.3, 5.9 Hz), 7.1–7.4
(5H, m); 13C NMR (75 MHz, CDCl3) ppm 31.6, 38.5,
72.5, 114.9, 125.8, 128.4, 128.4, 141.0, 141.8; FT-IR (neat)
m 3434, 2930, 2857, 1454, 1036, 992, 698 cmꢁ1. HPLC con-
ditions: Daicel Chiralcel OD-H; eluent: 3% 2-propanol in
hexane, flow rate, 1.0 mL/min, rt, retention time (min):
17.1 (R)-isomer, 26.0 (S)-isomer.
4.1.12. (R)-2-Methyl-1-p-tolylprop-2-en-1-ol 2l.3e Yield
22
70%. 93% ee. Colorless oil; ½aꢀD ¼ þ12:1 (c 0.2,
20
CHCl3) for (R)-2l with 86% ee {lit.3e ½aꢀD ¼ ꢁ12:1 (c
0.131, CHCl3) for (S)-2l with 96% ee}; 1H NMR
(300 MHz, CDCl3) d 1.61 (3H, s), 1.88 (1H, br s), 2.34
(3H, s), 4.95 (1H, br s), 5.10 (1H, br s), 5.20 (1H, br s),
7.15 (2H, d, J = 7.9 Hz), 7.26 (2H, d, J = 7.9 Hz); 13C
NMR (75 MHz, CDCl3) ppm 18.4, 21.1, 77.7, 110.8,
126.4, 129.1, 139.0, 142.8, 146.9; FT-IR (neat) m 3387,
4.1.8. (4E,3R)-1-Phenylpenta-1,4-dien-3-ol 2h.16 Yield
2971, 2922, 2863, 1655, 1512, 1449, 1375, 1047, 901 cmꢁ1
.
22
61%. 89% ee. Colorless oil; ½aꢀ ¼ ꢁ33:9 (c 1.0, CHCl3)
HPLC conditions: Daicel Chiralpak AS-H; eluent: 1.5%
ethanol in hexane, flow rate, 1.0 mL/min, rt, retention time
(min): 9.0 (R)-isomer, 11.1 (S)-isomer.
D
25
{lit.16 ½aꢀD ¼ þ38:5 (c 1.90, CHCl3) for (S)-2h with >95%
1
ee}; H NMR (300 MHz, CDCl3) d 1.61 (1H, br s), 4.82
(1H, br t, J = 6.1 Hz), 5.20 (1H, ddd, J = 10.5, 1.3,
1.3 Hz), 5.34 (1H, ddd, J = 17.2, 1.3, 1.3 Hz), 5.97 (1H,
ddd, J = 17.2, 10.5, 6.1), 6.23 (1H, dd, J = 16.0, 6.1 Hz),
6.62 (1H, d, J = 16.0 Hz), 7.2–7.5 (5H, m); 13C NMR
(75 MHz, CDCl3) ppm 73.8, 115.4, 126.5, 127.8, 128.6,
130.3, 130.8, 136.5, 139.2; FT-IR (neat) m 3505, 1451,
990, 966, 928, 752, 693 cmꢁ1. HPLC conditions: Daicel
Chiralpak AS-H; eluent: 3% 2-propanol in hexane, flow
rate, 1.0 mL/min, rt, retention time (min): 13.4 (R)-isomer,
15.9 (S)-isomer.
4.1.13.
2m.3d Yield 63%. 91% ee. Colorless oil; ½aꢀD ¼ þ56:7 (c
(R)-1-(4-Methoxyphenyl)-2-methylprop-2-en-1-ol
22
22
0.2, CHCl3) {lit.3d ½aꢀD ¼ ꢁ51:5 (c 1.6, CHCl3) for (S)-
2m with 92% ee}; 1H NMR (300 MHz, CDCl3) d 1.61
(3H, s), 1.89 (1H, br d, J = 2.7 Hz), 3.80 (3H, s), 4.94
(1H, br s), 5.08 (1H, br s), 5.20 (1H, br s), 6.8–6.9 (2H,
m), 7.2–7.3 (2H, m); 13C NMR (75 MHz, CDCl3) d 18.5,
55.3, 77.4, 110.6, 113.8, 127.8, 134.1, 147.0, 159.1; FT-IR
(neat) m 3424, 2838, 1611, 1512, 1248, 1173, 1036, 901,
825 cmꢁ1. HPLC conditions: Daicel Chiralcel OB-H;
eluent: 3% 2-propanol in hexane, flow rate, 1.0 mL/min,
rt, retention time (min): 19.4 (R)-isomer, 32.5 (S)-isomer.
4.1.9. (R)-2-Methyl-1-phenylprop-2-en-1-ol 2i.3d Yield
22
67%. 91% ee. Colorless oil; ½aꢀD ¼ þ26:6 (c 0.6, CHCl3)
23
{lit.3d ½aꢀD ¼ ꢁ27:4 (c 4.5, CHCl3) for (S)-2i with 89%
ee}; 1H NMR (300 MHz, CDCl3) d 1.61 (3H, s), 1.96
(1H, br s), 4.96 (1H, br s), 5.14 (1H, br s), 5.21 (1H, br
s), 7.2–7.4 (5H, m); 13C NMR (75 MHz, CDCl3) ppm
18.2, 77.9, 111.1, 126.4, 127.6, 128.4, 141.9, 146.8; FT-IR
4.1.14. (R)-2-Methyl-1-(naphthalen-2-yl)prop-2-en-1-ol 2n.22
22
Yield 61%. 92% ee. Colorless oil; ½aꢀD ¼ þ17:6 (c
1
2.2, CHCl3); H NMR (300 MHz, CDCl3) d 1.64 (3H, s),
2.05 (1H, br d, J = 3.4 Hz), 5.01 (1H, br s), 5.28 (1H, br
s), 5.31 (1H, br s), 7.4–7.5 (3H, m), 7.7–7.9 (4H, m); 13C
NMR (75 MHz, CDCl3) ppm 18.3, 78.0, 111.5, 124.4,
125.2, 125.9, 126.1, 127.7, 128.0, 128.2, 133.0, 133.3,
139.3, 146.7; FT-IR (neat) m 3426, 3056, 2973, 2920,
1653, 1601, 1508, 1049, 901, 816, 745 cmꢁ1. HPLC condi-
tions: Daicel Chiralpak AD-H; eluent: 4% 2-propanol in
hexane, flow rate, 0.7 mL/min, rt, retention time (min):
21.8 (R)-isomer, 25.6 (S)-isomer.
(neat) m 3406, 1655, 1493, 1450, 1375, 900, 839 cmꢁ1
.
HPLC conditions: Daicel Chiralpak AS-H; eluent: 3%
2-propanol in hexane, flow rate, 0.7 mL/min, rt, retention
time (min): 11.0 (R)-isomer, 12.2 (S)-isomer.
4.1.10. (R)-1-(4-Chlorophenyl)-2-methylprop-2-en-1-ol 2j.3e
22
Yield 80%. 90% ee. Colorless oil; ½aꢀD ¼ þ6:7 (c 0.4,
24
CHCl3) {lit.3e ½aꢀD ¼ ꢁ7:4 (c 1.6, CHCl3) for (S)-2j with
89% ee}; 1H NMR (300 MHz, CDCl3) d 1.59 (3H, s),
1.98 (1H, br d, J = 3.1 Hz), 4.96 (1H, br s), 5.12 (1H, br
s), 5.19 (1H, br s), 7.3–7.4 (4H, m); 13C NMR (75 MHz,
CDCl3) ppm 17.9, 77.2, 111.7, 127.8, 128.5, 133.3, 140.3,
146.5; FT-IR (neat) m 3391, 1655, 1491, 1439, 1406, 1375,
1091, 1041, 904, 844, 819, 790 cmꢁ1. HPLC conditions:
Daicel Chiralcel OB-H; eluent: 3% 2-propanol in hexane,
flow rate, 0.9 mL/min, rt, retention time (min): 10.1 (R-iso-
mer), 13.0 (S-isomer).
4.2. Synthesis of (R)-1-(4-bromophenyl)-3-methylbut-2-
en-1-ol 2o
Under a nitrogen atmosphere, dimethylzinc (1.0 M in
hexane; 1.5 mL, 1.5 mmol) was added to a solution of
tris(2-methylprop-1-enyl)bismuthine (188.0 mg, 0.50 mmol)
in Et2O (1.5 mL) at room temperature. The mixture was
heated at reflux for 1 h, then cooled to 0 °C. A solution
of (1R,2S)-PPP (13.1 mg, 0.06 mmol) in hexane (1.0 mL)
was added to the reaction mixture. A solution of p-bromo-
benzaldehyde (37.0 mg, 0.20 mmol) in hexane (1.5 mL) was
added to the mixture and the mixture was stirred for 12 h
at 0 °C. The reaction was quenched by adding aq
4.1.11. (R)-1-(4-Bromophenyl)-2-methylprop-2-en-1-ol 2k
22
Yield 62%. 94% ee. Colorless oil; ½aꢀD ¼ þ13:9 (c 1.8,
1
CHCl3); H NMR (300 MHz, CDCl3) d 1.59 (3H, s), 1.98
(1H, br d, J = 3.1 Hz,), 4.96 (1H, br s), 5.10 (1H, br s),