1018
T. Atago et al. / Tetrahedron: Asymmetry 20 (2009) 1015–1019
133.6, 133.9, 147.0, 154.2, 170.8. IR (KBr) 3062, 2949, 2930, 1748,
1620, 1593, 1509, 1393, 1263, 1219, 1136 cmꢄ1
(3H, m). 13C NMR (75 MHz, CDCl3) d 14.9, 19.6, 22.3, 29.1, 32.8,
34.3, 65.1, 115.3, 118.6, 121.9, 122.3, 123.7, 125.3, 126.2, 126.3,
126.5, 127.7, 128.0, 128.8, 129.1, 129.8, 131.6, 133.7, 133.8,
146.8, 154.2, 169.2. IR (KBr) 3459, 3057, 2988, 2953, 1740, 1620,
.
4.1.4. (1R,3R)- and (1S,3S)-[(R)-20-Ethoxy-1,10-binaphth-2-yl]3-
(20,20-dimethylethenyl)-2,2-dimethylcyclopropanecarboxylates
(1R,3R)-8 and (1S,3S)-8
1593, 1507, 1154 cmꢄ1
. HRMS (ESI) calcd for C30H26Cl2O3
(M+Na+) 527.1159, found 527.1155.
Following the procedure for the preparation of (1R)-6b, the
reaction using (1R*,3R*)-trans-chrysanthemic acid 10 (385 mg,
2.29 mmol), TsCl (437 mg, 2.29 mmol), N-methylimidazole
(470 mg, 5.73 mmol), and 5b (600 mg, 1.91 mmol), gave the crude
solids. These were collected using a glass filter, followed by being
washed with cooled hexane–AcOEt (15:1; 8 mL) to give the desired
product (1R,3R)-8 (284 mg, 32%).
(1S,3R)-9: Colorless crystals; mp 50–51 °C; Rf = 0.59 (hexane–
AcOEt = 5:1); ½a 2D5
ꢃ
¼ ꢄ40:2 (c 4.45, CHCl3). 1H NMR (300 MHz,
CDCl3) d 0.53 (3H, s), 0.88 (3H, s), 1.08 (3H, t, J = 6.9 Hz), 1.36
(1H, d, J = 5.5 Hz), 1.96 (1H, dd, J = 5.5, 8.3 Hz), 4.06 (2H, q,
J = 6.9 Hz), 5.41 (1H, d, J = 8.6 Hz), 7.08 (1H, d, J = 8.3 Hz), 7.13–
7.46 (7H, m), 7.82 (1H, d, J = 8.3 Hz), 7.87–7.99 (3H, m). 13C NMR
(75 MHz, CDCl3) d 14.8, 18.9, 22.1, 29.2, 32.7, 34.1, 65.0, 115.1,
118.4, 121.8, 123.5, 125.3, 125.4, 125.5, 126.2, 126.2, 126.4,
126.7, 127.6, 128.0, 128.8, 129.0, 129.7, 131.6, 133.6, 133.8,
146.8, 154.2, 169.0. IR (KBr) 3436, 3057, 2978, 2928, 1745, 1620,
(1R,3R)-8 (99% de based on 1H NMR): Colorless crystals; mp
165–167 °C; Rf = 0.70 (hexane–AcOEt = 5:1); ½a D24
¼ þ88:5 (c 1.00,
ꢃ
CHCl3). 1H NMR (300 MHz, CDCl3) d 0.90 (3H, s), 0.95 (3H, s),
1.04 (3H, t, J = 6.9 Hz), 1.10 (1H, d, J = 5.5 Hz), 1.36 (3H, s), 1.62
(3H, s), 1.69–1.76 (1H, m), 4.01 (2H, q, J = 7.2 Hz), 4.68 (1H, d,
J = 6.9 Hz), 7.12–7.33 (5H, m), 7.35–7.46 (3H, m), 7.82 (1H, d,
J = 8.3 Hz), 7.87–8.00 (3H, m). 13C NMR (75 MHz, CDCl3) d 14.9,
18.2, 20.0, 21.9, 25.4, 28.9, 32.8, 34.4, 65.1, 115.4, 118.8, 120.5,
122.2, 123.6, 125.2, 125.5, 126.1, 126.2, 126.4, 127.6, 128.0,
128.7, 129.1, 129.7, 131.5, 133.7, 133.8, 135.8, 147.0, 154.2,
170.6. IR (KBr) 3449, 2926, 2857, 1738, 1620, 1593, 1508, 1458,
1246, 1142, 1113, 862, 810 cmꢄ1. HRMS (ESI) calcd for C32H32O3
(M+Na+) 487.2249, found 487.2246.
1593, 1508, 1334, 1271, 1244, 1151, 1111 cmꢄ1
.
4.1.6. (1R,3S)-2,2-Dimethyl-3-(20,20-dichloroethenyl)
cyclopropanecarboxylic acid (1R,3S)-2 with recovery of (R)-
monoethyl ether of 1,10-binaphthol 5b
1 M KOH aqueous solution (25 mL) was added to a stirred solu-
tion of (1R,3S)-9 (3.89 g, 7.7 mmol) in THF (77 mL) and MeOH
(15 mL) at room temperature. After stirring at 60–65 °C for 2 h,
the mixture was cooled down and concentrated ca. 10 mL to give
the residue, which was extracted with ether (30 mL ꢂ 3). The aque-
ous phase was adjusted to ca. pH 1 using 6 M HCl aqueous solution,
which was re-extracted with AcOEt (30 mL ꢂ 3). The combined or-
ganic phase was washed with water, brine, dried (Na2SO4), and
concentrated to give the desired product (1R,3S)-2 (1.48 g, 92%).
The separated ether solution was washed with water, brine, dried
(Na2SO4), and concentrated to recover (1R)-5b (2.25 g, 93%).
(1R,3S)-2: Colorless crystals (99% ee); mp 70–71 °C;
(1S,3S)-8 (99% de based on 1H NMR): Colorless oil; mp 43–
44 °C; Rf = 0.70 (hexane–AcOEt = 5:1);
½
a 2D3
ꢃ
¼ ꢄ53:5 (c 1.35,
CHCl3). 1H NMR (300 MHz, CDCl3) d 0.48 (3H, s), 0.83 (3H, s),
1.08 (3H, t, J = 6.9 Hz), 1.17 (1H, d, J = 5.5 Hz), 1.55 (3H, s), 1.65
(3H, s), 1.75–1.88 (1H, m), 4.05 (2H, q, J = 6.9 Hz), 4.73 (1H, d,
J = 7.9 Hz), 7.09 (1H, d, J = 8.3), 7.13–7.32 (4H, m), 7.34–7.47
(3H, m), 7.81 (1H, d, J = 8.3 Hz), 7.87–7.99 (3H, m). 13C NMR
(75 MHz, CDCl3) d 14.9, 18.4, 19.3, 21.8, 25.5, 29.1, 32.5, 34.2,
65.1, 115.3, 118.8, 120.8, 122.2, 123.6, 125.2, 125.4, 125.7,
126.2, 126.2, 126.3, 127.5, 128.0, 128.7, 129.1, 129.6, 131.6,
133.7, 133.9, 135.4, 147.1, 154.2, 170.4. IR (KBr) 3420, 3059,
2978, 2926, 1743, 1622, 1593, 1508, 1460, 1431, 1244, 1136,
½
a 2D4
ꢃ
¼ þ35:7 (c 1.45, CHCl3). Lit., ½a D25
ꢃ
¼ þ36:3 (c 1.00, CHCl3).3b
4.1.7. (1R,3S)-2,2-Dimethyl-3-(20,20-dimethylethenyl)
cyclopropanecarboxylic acid (1R,3R)-1 and recovery of (R)-5b
Following the procedure for the preparation of (1R,3S)-2, the
reaction using (1R,3S)-8 (465 mg, 1.0 mmol) gave the desired
(1R,3R)-1 (151 mg, 90%) with the recovery of (R)-5b (292 g, 93%).
1111, 856, 808 cmꢄ1
.
4.1.5. (1R,3S)- and (1S,3R)-[(R)-20-Ethoxy-1,10binaphth-2-yl] 3-
(20,20-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylates
(1R,3S)-9 and (1S,3R)-9
Colorless oil (98% ee);
½
a 2D4
ꢃ
¼ þ25:1 (c 1.10, CHCl3). Lit.,
½
a 2D4
ꢃ
¼ þ25:9 (c 3.00, CHCl3).11
TsCl (6.33 g, 33.3 mmol) in CH3CN (25 mL) was added to a stir-
red solution of (1R*,3S*)-trans-(20,20-dichloroethenyl)-2,2-dimeth-
4.1.8. Determination of enantiomeric purity of (1R,3R)-1 using
the phenyl ester derivative
ylcyclopropanecarboxylic acid
2 (5.80 g, 27.7 mmol) and N-
A mixture of (1R,3R)-1 (25 mg, 0.15 mmol), SOCl2 (22 mg,
19 mmol), and a catalytic amount of DMF (1 drop) in hexane
(0.5 mL) was stirred at 60 °C for 1.5 h. Evaporation of the mixture
under reduced pressure gave the intermediary (1R,3R)-acid chlo-
ride (35 mg). This acid chloride in toluene (0.30 ml) was added to
a stirred solution of phenol (10 mg, 13 mmol) and pyridine
(13 mg, 0.15 mmol) in toluene (0.20 mL) at 0–5 °C, and the mixture
was stirred at room temperature for 2 h. Water was added to the
mixture, which was extracted with ether. The organic phase was
washed with water, brine, dried (Na2SO4), and concentrated. The
crude product obtained was purified by silica gel column chroma-
tography (hexane–AcOEt = 80:1) to give the phenyl ester of
(1R,3R)-1 (20 mg, 77% based on phenol).
methylimidazole (6.83 g, 83.2 mmol) in CH3CN (25 mL) at 0–5 °C
under an Ar atmosphere, followed by being stirred at the same
temperature for 0.5 h. Compound 5b (8.72 g, 27.7 mmol) in CH3CN
(25 mL) was added to the reaction mixture at 0–5 °C, followed by
being stirred at 20–25 °C for 2 h. The mixture was quenched with
water, which was extracted with AcOEt (20 mL ꢂ 3). The combined
organic phase was washed with 10% NaOH aqueous solution
(50 mL), water, brine, dried (Na2SO4), and concentrated. The crude
solids obtained were collected using a glass filter, followed by
being washed with cooled hexane–AcOEt (15:1; 120 mL). The ob-
tained solids were recrystallized from AcOEt to give the desired
product (1R,3S)-9 (5.33 g, 36%). The filtrate was concentrated and
purified by SiO2 column chromatography (hexane–AcOEt = 10:1)
to give pure (1S,3R)-9.
Colorless oil; ½a D24
ꢃ
¼ þ21:8 (c 0.65, CHCl3). 1H NMR (300 MHz,
CDCl3) d 1.22 (3H, s), 1.35 (3H, s), 1.63 (1H, d, J = 5.5 Hz), 1.74
(3H, s), 1.75 (3H, s), 2.18 (1H, dd, J = 5.5, 7.6 Hz), 4.97 (1H, d,
J = 7.6 Hz), 7.04–7.11 (2H, m), 7.15–7.25 (1H, m), 7.31–7.40 (2H,
m). 13C NMR (75 MHz, CDCl3) d 18.5, 20.4, 22.2, 25.6, 29.6, 33.5,
34.6, 120.8, 121.7, 125.5, 129.3, 136.0, 151.0, 171.1. IR (KBr)
(1R,3S)-9: Colorless crystals (97% de); mp 158–160 °C; Rf = 0.59
(hexane–AcOEt = 5:1);
½
a 2D9
ꢃ
¼ þ77:4 (c 1.00, CHCl3). 1H NMR
(300 MHz, CDCl3)
d
0.94 (3H, s), 0.96 (3H, s), 1.03 (3H, t,
J = 6.9 Hz), 1.29 (1H, d, J = 5.5 Hz), 1.86 (1H, dd, J = 5.5, 7.9 Hz),
4.01 (2H, q, J = 6.9 Hz), 5.35 (1H, d, J = 7.9 Hz), 7.14 (1H, d,
J = 8.3 Hz), 7.18–7.49 (7H, m), 7.84 (1H, d, J = 8.3 Hz), 7.88–8.01
3355, 3044, 2926, 1746, 1595, 1493, 1198, 1134, 1111 cmꢄ1
.