Concurrent Induction of Two Chiral Centers
J . Org. Chem., Vol. 65, No. 18, 2000 5815
18.5 Hz, 1H); EIMS m/z 262 (M+, 37), 130 (100); HRMS calcd
for C19H18O1 (M+) 262.1358, found 262.1396. Cyclization of 4b
by the neutral Rh[(S)-BINAP]Cl (0.50 equiv) afforded (3R,4S)-
cis/trans ) 2/98, >95% ee) as a colorless oil. [R]23 -132.1° (c
D
1.11, CHCl3).
The enantiomeric excesses of 10c were determined by 1H
(-)-9b (30% yield, cis/trans ) >99/0) as a colorless oil. [R]23
NMR and 13C NMR spectra of the acetals derived from (R,R)-
D
1
-65.4° (c 0.75, CHCl3).
2,3-butandiol. The 270 MHz H NMR spectrum of the butane-
The enantiomeric excesses of 9b were determined by 1H
NMR spectra of acetals derived from (R,R)-2,3-butandiol. The
1H NMR (270 MHz) spectrum of the butanediol acetal of (()-
9b showed the olefin proton signals at δ 5.01 (s, 0.5H), 4.99
(s, 0.5H) in the ratio of 1 to 1, and also 4.76 (br s, 0.5H), 4.69
(br s, 0.5H) in the ratio of 1 to 1, while the corresponding
signals from (+)-9b were only observed at δ 4.99 (s, 1H) and
4.69 (br s, 1H), and those from (-)-9b were observed at δ 5.01
(s, 1H) and 4.76 (br s, 1H), only. The enantiomeric excesses
were also supported by 13C NMR spectra. (R,R)-2,3-Butanediol
acetal of (+)-9b: 13C NMR (68 MHz, CDCl3) δ 148.0, 142.9,
142.0, 128.8-125.7 (aromatic-C10), 115.7, 112.9, 78.7, 78.4,
46.1, 45.9, 45.0, 41.2, 17.2, 16.8; (R,R)-2,3-Butanediol acetal
of (-)-9b: 13C NMR (68 MHz, CDCl3) δ 148.5, 142.9, 142.1,
128.7-125.7 (aromatic-C10), 115.6, 112.9, 79.0, 78.3, 45.8, 45.5,
45.0, 41.8, 17.3, 17.2.
diol acetal derived from (+)-10c showed the olefin proton
signals at δ 4.843 (br s, 1H) and 4.745 (br s, 1H), while those
from (-)-10c showed the signals at δ 4.851 (br s, 1H) and 4.741
(br s, 1H). The enantiomeric excesses were also conformed by
13C NMR spectra. (R,R)-2,3-Butanediol acetal of (+)-10c: 13C
NMR (68 MHz, CDCl3) δ 149.0, 115.4, 110.1, 78.2, 78.2, 51.3,
46.0, 45.3, 44.5, 43.4, 39.7, 26.8, 26.2, 24.2, 22.7, 22.5, 21.5,
16.9, 16.9; (R,R)-2,3-Butanediol acetal of (-)-10c: 13C NMR
(68 MHz, CDCl3) δ 149.2, 115.5, 110.1, 78.3, 78.2, 51.1, 45.6,
45.0, 44.3, 43.8, 39.4, 26.8, 26.2, 24.1, 22.6, 22.5, 21.6, 17.3,
17.3.
cis-3,4-Dim eth yl-3-isop r op en ylcyclop en ta n on e (17a ).
Cyclization of 8a by the neutral Rh[(R)-BINAP]Cl (0.50 equiv)
afforded (3S,4R)-(+)-17a (5% yield, cis/trans ) 95/5, 87% ee)
as a colorless oil. [R]23D +13.1° (c 0.61, CHCl3); IR (neat) 1740,
1640 cm-1; 1H NMR (270 MHz, CDCl3) δ 4.84 (m, 1H), 4.66 (s,
1H), 2.62 (m, 1H), 2.55 (m, 1H), 2.26 (m, 1H), 2.04 (m, 1H),
1.98 (m, 1H), 1.78 (br s, 3H), 1.17 (s, 3H), 0.88 (d, J ) 6.9 Hz,
3H); 13C NMR (68 MHz, CDCl3) δ 219.0, 148.5, 110.6, 47.9,
47.8, 45.0, 38.1, 26.2, 19.6, 17.4; EIMS m/z 153 (M+ + 1, 3),
152 (M+, 21), 110 (9), 96 (14), 82 (100); HRMS calcd for
tr a n s-4-P h en yl-3-(1-ph en ylvin yl)cyclopen tan on e (10b).
Cyclization of 4b by the cationic Rh[(R)-BINAP]ClO4 (0.05
equiv) mainly afforded (3S,4S)-(+)-10b (70% yield, cis/trans
) 17/83, >95% ee) as a colorless oil. [R]23 +50.1° (c 1.14,
D
CHCl3); IR (neat) 1740, 1630 cm-1; 1H NMR (270 MHz, CDCl3)
δ 6.69-7.38 (m, 10H), 5.22 (s, 0.83H), 5.14 (s, 0.83H), 5.12 (s,
0.17H), 4.66 (s, 0.17H), 3.93 (m, 0.17H), 3.76 (br q, J ) 6.2
Hz, 0.17H), 3.40-3.58 (m, 1.66H), 2.66-2.86 (m, 2H), 2.25-
2.57 (m, 2H); EIMS m/z 262 (M+, 38), 220 (3), 205 (6), 130 (100).
Purification by HPLC afforded (3S,4S)-(+)-10b as colorless
crystals. mp 78.0-80.0 °C (recryst. from hexane). Anal. Calcd
for C19H18O1: C, 86.99; H, 6.92. Found: C, 86.70; H, 6.90.
Cyclization of 4a by the cationic Rh[(S)-BINAP]ClO4 (0.05
equiv) mainly afforded (3R,4R)-(-)-10b (76% yield, cis/trans
C
10H16O1 (M+) 152.1201, found 152.1197. Cyclization of 8a by
the neutral Rh[(S)-BINAP]Cl (0.50 equiv) afforded (3R,4S)-
(-)-17a (5% yield, cis/trans ) 95/5, 88% ee) as a colorless oil.
[R]23 -15.0° (c 0.53, CHCl3).
D
The enantiomeric excesses of 17a were determined by 1H
NMR spectra of acetals derived from (R,R)-2,3-butandiol. The
1H NMR spectrum of the butanediol acetal of (()-17a showed
the olefin proton signals at δ 4.76 (m, 0.5H), 4.73 (m, 0.5H) in
the ratio of 1 to 1, and also 4.69 (s, 0.5H), 4.66 (s, 0.5H) in the
ratio of 1 to 1, while the corresponding signals from (+)-17a
cyclized by Rh[(R)-BINAP]Cl were observed at δ 4.73 (m,
0.94H) and 4.66 (s, 0.94H), and also at δ 4.76 (m, 0.06H) and
4.69 (s, 0.06H). The signals derived from (-)-17a cyclized by
Rh[(S)-BINAP]Cl were observed at δ 4.76 (m, 0.94H) and 4.69
(s, 0.94H), and also at δ 4.73 (m, 0.06H) and 4.66 (s, 0.06H).
The enantiomeric excesses were also supported by 13C NMR
spectra. (R,R)-2,3-Butanediol acetal of (+)-17a : 13C NMR (68
MHz, CDCl3) δ 150.4, 116.7, 109.5, 78.0, 77.9, 49.6, 47.2, 45.9,
40.2, 26.1, 19.9, 17.3, 17.1, 17.0; (R,R)-2,3-Butanediol acetal
of (-)-17a : 13C NMR (68 MHz, CDCl3) δ 150.2, 116.5, 110.0,
78.3, 78.3, 49.3, 48.5, 46.0, 40.8, 26.4, 20.4, 17.4, 17.4, 17.0.
tr a n s-3,4-Dim eth yl-3-isopr open ylcyclopen tan on e (18a).
Cyclization of 8a by the cationic Rh[(R)-BINAP]ClO4 (0.05
equiv) afforded (3S,4S)-(+)-18a (83% yield, cis/trans ) 2/98,
) 16/84, >95% ee) as a colorless oil. [R]23 - 51.1° (c 1.30,
D
CHCl3).
The enantiomeric excesses of 10b were determined by 1H
NMR and 13C NMR spectra of the acetals derived from (R,R)-
1
2,3-butandiol. The 270 MHz H NMR spectrum of the (R,R)-
butanediol acetal derived from (+)-10b showed the olefin
proton signals at δ 5.131 (s, 1H) and 5.100 (s, 1H), while those
from (-)-10b showed the signals at δ 5.136 (s, 1H) and 5.113
(s, 1H). The enantiomeric excesses were also conformed by 13
C
NMR spectra. (R,R)-2,3-Butanediol acetal of (+)-10b: 13C NMR
(125.8 MHz, CDCl3) δ 149.9, 142.9, 142.4, 128.7-125.9 (aro-
matic-C10), 114.3, 113.0, 78.4, 78.3, 49.4, 48.5, 48.2, 46.7, 16.9,
16.9; (R,R)-2,3-Butanediol acetal of (-)-10b: 13C NMR (125.8
MHz, CDCl3) δ 150.2, 143.3, 142.3, 128.8-125.7 (aromatic-
C
10), 114.5, 112.9, 78.4, 78.4, 49.5, 48.3, 47.8, 46.4, 17.2, 17.2.
>95% ee) as a colorless oil. [R]23 +104.0° (c 1.30, CHCl3); IR
D
(neat) 1740, 1630 cm-1; 1H NMR (500 MHz, CDCl3) δ 4.89 (m,
1H), 4.84 (br s, 1H), 2.45-2.52 (m, 2H), 2.43 (d, J ) 18.8 Hz,
1H), 2.12 (d, J ) 18.8 Hz, 1H), 1.98 (m, 1H), 1.79 (br s, 3H),
1.05 (s, 3H), 0.99 (d, J ) 6.6 Hz, 3H); 13C NMR (68 MHz,
CDCl3) δ 218.0, 148.7, 111.2, 52.3, 46.7, 44.3, 36.3, 19.9, 18.8,
14.4; EIMS m/z 152 (M+, 7), 110 (3), 96 (19), 82 (100); HRMS
calcd for C10H16O1 (M+) 152.1201, found 152.1204. Cyclization
of 8a by the cationic Rh[(S)-BINAP]ClO4 (0.05 equiv) afforded
(3R,4R)-(-)-18a (75% yield, cis/trans ) 2/98, >95% ee) as a
cis-4-Isobu tyl-3-(1-isobu tylvin yl)cyclop en ta n on e (9c).
Cyclization of 4c by Wilkinson complex (0.50 equiv) afforded
(()-9c (67% yield, cis/trans ) 98/2) as a colorless oil. IR (neat)
1
1740, 1640 cm-1; H NMR (270 MHz, CDCl3) δ 4.92 (s, 1H),
4.71 (s, 1H), 2.86 (m, 1H), 2.48 (m, 1H), 2.15-2.40 (m, 4H),
2.05 (m, 1H), 1.74-1.92 (m, 2H), 1.41-1.67 (m, 2H), 1.10 (m,
1H), 0.80-1.00 (m, 12H); 13C NMR (68 MHz, CDCl3) δ 219.0,
146.8, 111.5, 45.4, 45.0, 44.7, 40.5, 37.5, 35.5, 26.3, 25.9, 24.1,
23.4, 21.9, 21.3; EIMS m/z 222 (M+, 11), 139 (39), 111 (65), 95
(100), 83 (88), 68 (91); HRMS calcd for C15H26O1 (M+) 222.1984,
found 222.1980.
colorless oil. [R]23 -111.0° (c 1.30, CHCl3).
D
The enantiomeric excesses of 18a were determined by 1H
NMR spectra of acetals derived from (R,R)-2,3-butandiol. The
1H NMR spectrum of the butanediol acetal of (+)-18a cyclized
by Rh[(R)-BINAP]Cl showed the olefin proton signals at δ 4.79
(m, 1H) and 4.77 (br s, 1H), and methyl proton signal at δ
1.03 (s, 3H), while those from (-)-18a cyclized by Rh[(S)-
BINAP]Cl were observed at δ 4.77-4.78 (m, 2H) and methyl
proton signal at δ 1.04 (s, 3H). The enantiomeric excesses were
also supported by 13C NMR spectra. (R,R)-2,3-Butanediol
acetal of (+)-18a : 13C NMR (68 MHz, CDCl3) δ 150.6, 115.2,
109.8, 78.3, 77.8, 52.1, 47.7, 46.0, 38.0, 20.0, 18.6, 17.1, 16.9,
13.6; (R,R)-2,3-Butanediol acetal of (-)-18a : 13C NMR (68
MHz, CDCl3) δ 150.7, 115.2, 109.7, 78.6, 77.9, 52.0, 47.5, 45.9,
38.0, 20.0, 19.3, 17.4, 17.3, 13.7.
tr a n s-4-Isob u t yl-3-(1-isob u t ylvin yl)cyclop en t a n on e
(10c). Cyclization of 4c by the cationic Rh[(R)-BINAP]ClO4
(0.05 equiv) afforded (3S,4S)-(+)-10c (74% yield, cis/trans )
2/98, >95% ee) as a colorless oil. [R]23D +141.5° (c 1.07, CHCl3);
IR (neat) 1740, 1640 cm-1; 1H NMR (270 MHz, CDCl3) δ 4.91
(s, 1H), 4.86 (br s, 1H), 2.31-2.61 (m, 3H), 2.04-2.30 (m, 2H),
1.71-1.95 (m, 4H), 1.41-1.66 (m, 2H), 1.11 (m, 1H), 0.80-
1.00 (m, 12H); 13C NMR (68 MHz, CDCl3) δ 217.9, 148.1, 110.9,
49.4, 45.5, 45.1, 44.4, 43.6, 38.6, 26.7, 26.3, 23.9, 22.6, 22.5,
21.5; EIMS m/z 222 (M+, 23), 165 (14), 139 (29), 110 (77), 95
(100), 83 (87), 68 (81); HRMS calcd for C15H26O1 (M+) 222.1984,
found 222.1986. Cyclization of 4c by the cationic Rh[(S)-
BINAP]ClO4 (0.05 equiv) afforded (3R,4R)-(-)-10c (77% yield,