2412 J . Org. Chem., Vol. 66, No. 7, 2001
Arjona et al.
allowed to react and afforded 141 mg of (-)-58 as a colorless
oil after purification by chromatography eluting with hexanes/
ethyl acetate (2:1) (90%): [R]D ) -107.6° (0.01 M, CH2Cl2); IR
(CCl4) υ 3650, 1600, 1470, 1110; 1H NMR (CDCl3, 300 MHz) δ
1.10 (d, 3 H, J ) 7.0 Hz), 1.26 (d, 3 H, J ) 7.0 Hz), 1.83-1.89
(m, 1 H), 2.57 (q, 1 H, J ) 7.1 Hz), 3.10 (d, 1 H, J ) 9.2 Hz),
3.62 (m, 1 H), 4.08 (t, 1 H, J ) 4.8 Hz), 4.69 (syst. AB, 2 H,
J AB) 12.1 Hz), 7.29 (dd, 1 H, J ) 4.8, 2.2 Hz), 7.33-7.40 (m,
5 H), 7.52 (t, 2 H, J ) 7.7 Hz), 7.60 (t, 1 H, J ) 7.6 Hz), 7.79
(d, 2 H, J ) 7.7 Hz); 13C NMR (CDCl3, 75 MHz) δ 13.8, 15.0,
37.1, 38.0, 72.8, 73.9, 74.2, 127.5, 127.9, 128.3, 128.6, 129.2,
133.2, 135.7, 137.3, 140.6, 145.3. Anal. Calcd for C21H24O4S:
C, 67.90; H, 6.52. Found: C, 67.74; H, 6.45.
(3S,4R,5R,6R)-3-(Ben zyloxy)-5-(ben zoyloxy)-1-(p h en yl-
su lfon yl)-4,6-d im eth yl cycloh ex-1-en e, (-)-60. In a manner
similar to that described for (+)-57, 101 mg (0.27 mmol) of
(-)-58 was allowed to react and afforded 116 mg of (-)-60 as
a white solid after purification by chromatography eluting with
hexanes/ethyl acetate (5:1) (90%): [R]D ) -59.6° (0.01 M,
CH2Cl2); mp 92-93 °C IR (KBr) υ 1720, 1580, 1470, 1150; 1H
NMR (CDCl3, 300 MHz) δ 1.10 (d, 3 H, J ) 7.3 Hz), 1.15 (d, 3
H, J ) 7.1 Hz), 2.40 (qd, 1 H, J ) 7.1, 2.9 Hz), 2.93-3.01 (m,
1 H), 4.25 (td, 1 H, J ) 3.0, 2.0 Hz), 4.69 (s, 2 H), 5.27 (dd, 1
H, J ) 5.1, 3.0 Hz), 7.29 (d, 1 H, J ) 2.0 Hz), 7.34-7.52 (m, 7
H), 7.59-7.67 (m, 4 H), 7.85 (d, 2 H, J ) 6.8 Hz), 8.00 (d, 2 H,
J ) 7.1 Hz); 13C NMR (CDCl3, 75 MHz) δ 12.0, 14.1, 33.9, 35.7,
72.2, 72.8, 73.9, 127.5, 127.7, 128.2, 128.4, 129.1, 129.2, 129.7,
130.1, 132.9, 133.2, 133.7, 137.7, 141.3, 142.0, 171.8. Anal.
Calcd for C28H28O5S: C, 70.59; H, 5.88. Found: C, 70.56; H,
5.83.
(CDCl3, 75 MHz) δ 11.2, 17.6, 31.1, 33.1, 47.6, 52.3, 69.9, 82.4,
129.5, 129.7, 129.9, 133.0, 133.2, 136.9, 137.5, 138.6, 168.5,
173.2, 199.5. Anal. Calcd for C23H26O6: C, 69.35; H, 6.53.
Found: C, 69.30; H, 6.46.
(3S ,4R ,5R ,6S )-3-(Be n zyloxy)-5-(b e n zoyloxy)-4,6-d i-
m eth ylcycloh ex-1-en e, (+)-64. To a solution of 25 mg of (+)-
56 (0.11 mmol) in 1 mL of toluene were added 0.16 mL (0.16
mmol, 1 M solution in THF) of PMe3, 20 mg (0.16 mmol) of
BzOH, and 0.025 mL (0.16 mmol) of DEAD, respectively. The
reaction was stirred for 12 h and then concentrated under
reduced pressure. Purification via flash chromatography elut-
ing with hexanes/ethyl acetate (10:1) produced 27 mg of (+)-
64 (74%) as a colorless oil: [R]D ) +50.6° (0.01 M, CH2Cl2); IR
(CCl4) υ 2860, 1730, 1440, 1050; 1H NMR (CDCl3, 300 MHz) δ
1.02 (d, 3 H, J ) 4.7 Hz), 1.06 (d, 3 H, J ) 4.2 Hz), 2.13 (tq, 1
H, J ) 6.2, 4.2 Hz), 2.53-2.61 (m, 1 H), 3.91 (ddd, 1 H, J )
6.2, 2.0, 1.2 Hz), 4.61 (syst. AB, 2 H, J AB) 7.5 Hz), 4.89 (dd, 1
H, J ) 7.6, 6.2 Hz), 5.61 (dt, 1 H, J ) 6.8, 1.2 Hz), 5.84 (dt, 1
H, J ) 6.8, 2.0 Hz), 7.29-7.38 (m, 7 H), 7.48 (t, 1 H, J ) 6.5
Hz), 8.09 (d, 2 H, J ) 6.5 Hz); 13C NMR (CDCl3, 75 MHz) δ
14.0, 18.1, 37.2, 40.6, 70.7, 78.5, 80.4, 127.7, 127.9, 128.4, 128.6,
129.7, 130.2, 132.6, 133.0, 136.1, 138.4, 166.5. Anal. Calcd for
C
22H34O6Si: C, 62.56; H, 8.05. Found: C, 62.47; H, 7.96. Anal.
Calcd for C22H24O3: C, 78.57; H, 7.14. Found: C, 78.41; H,
7.04.
(2R,3S,4S,5R)-Met h yl 5-(Ben zyloxy)-3-(b en zoyloxy)-
2,4-d im eth yl-6-oxoh exa n oa te, (-)-66. In a manner similar
to that described for 30, 21 mg (0.062 mmol) of (+)-64 were
allowed to react and afforded 16 mg of (-)-66 as a colorless
oil after purification by chromatography eluting with hexanes/
ethyl acetate (5:1) (64%): [R]D ) -10.4° (0.02 M, CH2Cl2); IR
(CCl4) υ 2840, 2780, 1750, 1200; 1H NMR (CDCl3, 300 MHz) δ
0.88 (d, 3 H, J ) 6.1 Hz), 1.21 (d, 3 H, J ) 5.7 Hz), 2.04-2.16
(m, 1 H), 2.88 (qd, 1 H, J ) 5.7, 3.0 Hz), 3.70 (s, 3 H), 4.13 (dd,
1 H, J ) 4.5, 1.5 Hz), 4.58 (syst. AB, 2 H, J AB) 8.1 Hz), 5.72
(dd, 1 H, J ) 5.1, 3.0 Hz), 7.32-7.49 (m, 7 H), 7.60 (t, 1 H, J
) 5.7 Hz), 7.98 (d, 2 H, J ) 5.7 Hz), 9.67 (d, 1 H, J ) 1.0 Hz);
13C NMR (CDCl3, 75 MHz) δ 15.2, 19.2, 28.5, 31.3, 45.2, 52.3,
76.3, 85.1, 128.1, 129.5, 129.6, 130.4, 133.8, 134.2, 135.1, 135.3,
167.9, 175.3, 201.3. Anal. Calcd for C23H26O6: C, 69.35; H, 6.53.
Found: C, 69.23; H, 6.38.
(3S,4R,5S,6R)-3-(Ben zyloxy)-5-(ben zoyloxy)-1-(p h en yl-
su lfon yl)-4,6-d im eth ylcycloh ex-1-en e, (-)-67. In a manner
similar to that described for (+)-64, 161 mg (0.43 mmol) of
(-)-58 was allowed to react and afforded 101 mg of (-)-67 as
a colorless oil after purification by chromatography eluting
with hexanes/ethyl acetate (8:1) (49%): [R]D ) -46.5° (0.02
M, CH2Cl2);IR (CCl4) υ 2980, 1730, 1580, 1210; 1H NMR
(CDCl3, 300 MHz) δ 1.00 (d, 3 H, J ) 5.3 Hz), 1.22 (d, 3 H, J
) 5.0 Hz), 2.53 (sext, 1 H, J ) 5.0 Hz), 3.04 (m, 1 H), 4.35 (dd,
1 H, J ) 5.0, 2.3 Hz), 4.41 (syst. AB, 2 H, J AB ) 7.5 Hz), 5.65
(dd, 1 H, J ) 7.6, 5.1 Hz), 7.13 (d, 1 H, J ) 2.3 Hz), 7.30-7.43
(m, 7 H), 7.53-7.63 (m, 6 H), 7.86 (d, 2 H, J ) 4.9 Hz); 13C
NMR (CDCl3, 75 MHz) δ 11.0, 19.3, 31.1, 32.0, 49.2, 68.1, 75.1,
125.7, 127.5, 127.7, 128.3, 128.8, 129.0, 133.2, 133.8, 137.5,
137.6, 137.8, 139.5, 140.1, 146.9, 173.1. Anal. Calcd for
(3R ,4R ,5S ,6S )-3-(Be n zyloxy)-5-(b e n zoyloxy)-4,6-d i-
m eth ylcycloh ex-1-en e, (-)-61. In a manner similar to that
described for (+)-56 (method A), 45 mg (0.094 mmol) of (-)-
60 was allowed to react and afforded 18 mg of (-)-61 as a
colorless oil after purification by chromatography eluting with
hexanes/ethyl acetate (15:1) (57%): [R]D ) -11.5° (0.02 M,
1
CH2Cl2); IR (CCl4) υ 1730, 1320, 1050, 840; H NMR (CDCl3,
300 MHz) δ 1.07 (d, 3 H, J ) 6.0 Hz), 1.18 (d, 3 H, J ) 5.7
Hz), 2.23 (qdd, 1 H, J ) 5.7, 3.3, 1.2 Hz), 2.56-2.64 (m, 1 H),
3.92 (dd, 1 H, J ) 3.3, 2.6 Hz), 4.65 (Syst. AB, 2 H, J AB) 7.6
Hz), 5.38 (dd, 1 H, J ) 3.0, 1.2 Hz), 5.63 (dt, 1 H, J ) 6.8, 1.2
Hz), 6.07 (ddd, 1 H, J ) 6.8, 2.6, 1.7 Hz), 7.21-7.36 (m, 7 H),
7.47 (t, 1 H, J ) 5.3 Hz), 8.07 (d, 2 H, J ) 5.4 Hz); 13C NMR
(CDCl3, 75 MHz) δ 15.3, 21.2, 30.5, 33.1, 72.9, 74.2, 81.3, 126.5,
126.9, 127.4, 128.9, 129.9, 133.3, 135.5, 136.7, 138.4, 139.5,
173.3. Anal. Calcd for C22H24O3: C, 78.57; H, 7.14. Found: C,
78.46; H, 7.06.
(2R,3R,4S,5R)-Met h yl 5-(Ben zyloxy)-3-(b en zoyloxy)-
2,4-d im eth yl-6-oxoh exa n oa te (+)-62. In a manner similar
to that described for 30, 10 mg (0.030 mmol) of (+)-57 were
allowed to react and afforded 7 mg of (+)-62 as a colorless oil
after purification by chromatography eluting with hexanes/
ethyl acetate (5:1) (67%): [R]D ) +13.0° (0.03 M, CH2Cl2); IR
(CCl4) υ 2840, 2780, 1720, 1310; 1H NMR (CDCl3, 300 MHz) δ
1.03 (d, 3 H, J ) 7.3 Hz), 1.24 (d, 3 H, J ) 7.0 Hz), 2.56-2.62
(m, 1 H), 3.06 (qd, 1 H, J ) 7.0, 3.6 Hz), 3.72 (s, 3 H), 3.82 (m,
1 H), 4.50 (syst. AB, 2 H, J AB) 10.8 Hz), 5.51 (dd, 1 H, J )
9.0, 3.6 Hz), 7.24-7.56 (m, 7 H), 7.59 (t, 1 H, J ) 7.1 Hz), 8.03
(d, 2 H, J ) 6.9 Hz), 9.72 (d, 1 H, J ) 1.0 Hz); 13C NMR (CDCl3,
75 MHz) δ 14.9, 21.2, 29.7, 37.5, 41.1, 51.8, 73.4, 83.4, 127.9,
128.2, 128.4, 128.5, 129.8, 130.1, 133.0, 136.1, 166.5, 177.0,
194.3. Anal. Calcd for C23H26O6: C, 69.35; H, 6.53. Found: C,
69.41; H, 6.58.
(2R,3R,4S,5S)-Met h yl 5-(Ben zyloxy)-3-(b en zoyloxy)-
2,4-d im eth yl-6-oxoh exa n oa te (+)-63. In a manner similar
to that described for 30, 18 mg (0.053 mmol) of (-)-61 were
allowed to react and afforded 13 mg of (+)-63 as a colorless
oil after purification by chromatography eluting with hexanes/
ethyl acetate (5:1) (61%): [R]D ) +19.3° (0.03 M, CH2Cl2); IR
(CCl4) υ 2980, 2780, 1720, 1200; 1H NMR (CDCl3, 300 MHz) δ
1.08 (d, 3 H, J ) 6.7 Hz), 1.20 (d, 3 H, J ) 6.6 Hz), 2.00-2.05
(m, 1 H), 2.99-3.06 (m, 1 H), 3.69 (s, 3 H), 3.74 (dd, 1 H, J )
5.2, 1.3 Hz), 4.62 (syst. AB, 2 H, J AB) 8.0 Hz), 5.54 (dd, 1 H,
J ) 5.9, 2.9 Hz), 7.32-7.51 (m, 7 H), 7.60 (t, 1 H, J ) 6.9 Hz),
8.11 (d, 2 H, J ) 6.9 Hz), 9.54 (d, 1 H, J ) 1.3 Hz); 13C NMR
C
28H28O5S: C, 70.59; H, 5.88. Found: C, 70.47; H, 5.80.
(3R ,4R ,5R ,6S )-3-(Be n zyloxy)-5-(b e n zoyloxy)-4,6-d i-
m eth ylcycloh ex-1-en e, (+)-68. In a manner similar to that
described for (+)-56 (method A), 70 mg (0.15 mmol) of (-)-67
was allowed to react and afforded 23 mg of (+)-68 as a colorless
oil after purification by chromatography eluting with hexanes/
ethyl acetate (15:1) (46%): [R]D ) +15.8° (0.02 M, CH2Cl2); IR
(CCl4) υ 2960, 1730, 1470, 1150; 1H NMR (CDCl3, 300 MHz) δ
0.95 (d, 3 H, J ) 7.3 Hz), 1.20 (d, 3 H, J ) 7.1 Hz), 1.67 (m, 1
H), 2.47 (m, 1 H), 3.87 (dd, 1 H, J ) 3.9, 1.2 Hz), 4.43 (syst.
AB, 2 H, J AB) 11.9 Hz), 5.67 (ddt, 1 H, J ) 15.8, 3.9, 1.2 Hz),
5.78 (m, 1 H), 5.79 (dt, 1 H, J ) 15.8, 1.2 Hz), 7.28-7.36 (m,
5 H), 7.48-7.61 (m, 3 H), 7.86 (dt, 2 H, J ) 8.3, 1.7 Hz); 13C
NMR (CDCl3, 75 MHz) δ 13.2, 18.2, 25.9, 33.1, 66.6, 74.5, 81.3,
127.5, 129.8, 129.9, 130.1, 135.9, 136.8, 137.5, 138.3, 144.0,
146.3, 170.0. Anal. Calcd for C22H24O3: C, 78.57; H, 7.14.
Found: C, 78.49; H, 7.10.
(2R,3S,4S,5S)-Meth yl 5-(Ben zyloxy)-3-(ben zoyloxy)-2,4-
d im eth yl-6-oxoh exa n oa te, (+)-69. In a manner similar to