4 cm3). The combined extract was washed with brine (5 cm3),
dried (MgSO4) and evaporated under reduced pressure. The
residue was chromatographed (SiO2, EtOAc–light petroleum,
20 : 80 to 70 : 30) to give three diols A (5 mg, 12%), B (18 mg,
40%) and C (19 mg, 42%); A: Rf(EtOAc–light petroleum, 7 : 3)
0.64; νmax(CDCl3)/cmϪ1 3649 (OH), 1739, 1255 (SiMe), 1183,
1108 (SiPh), 1043 and 882; δH(500 MHz, CDCl3) 7.63–7.57
(2 H, m, m-Ph), 7.34–7.30 (3H, m, o,p-Ph), 4.09 (1 H, br s,
SiCHCHCHOH), 3.04 (1 H, tt, J 10.6 and 4.2, CHCHCH2-
CHOH), 1.99–0.54 (16 H, series of m’s, MeCHCH2, CH2CH-
(Si)CHCHCH2 and CH2CH2CH2CHO), 0.79 (3 H, d, J 6.4,
MeCH), 0.43 (3 H, s, SiMeAMeB) and 0.39 (3 H, s, SiMeAMeB);
δC(125 MHz, CDCl3) 141.6ϩ, 134.0Ϫ, 128.5Ϫ, 127.6Ϫ, 70.3Ϫ,
66.4Ϫ, 51.2Ϫ, 42.9ϩ, 41.3ϩ, 37.5ϩ, 35.8Ϫ, 35.3ϩ, 29.6ϩ,
24.1Ϫ, 23.8ϩ, 23.6Ϫ, 22.3Ϫ, Ϫ0.0Ϫ and Ϫ0.5Ϫ; m/z (ESI) 369
(100%, Mϩ ϩ Naϩ) (Found: Mϩ ϩ Naϩ 369.2233, C21H34O2Si
requires M ϩ Na, 346.2328); B: Rf(EtOAc–light petroleum, 7 : 3)
0.40; νmax(CDCl3)/cmϪ1 3608 (OH), 3461 (OH), 1793, 1640, 1601,
1251 (SiMe), 1166 (SiPh) and 1095; δH(500 MHz, CDCl3) 7.52–
7.30 (5 H, m, Ph), 3.83 (1 H, dt, J 11.1 and 4.3, SiCHCHCHOH),
3.54 (1 H, tt, J 10.7 and 4.2, CHCHCH2CHOH), 2.05–0.92 (16
H, series of m’s, CH2CH(Me)CH2CH(Si)CHCHCH2CH2CH2-
CHCH2), 0.90 (3 H, d, J 6.2, MeCH), 0.33 (3 H, s, SiMeAMeB)
and 0.31 (3 H, s, SiMeAMeB); δC(125 MHz, CDCl3) 139.2ϩ,
133.6Ϫ, 128.7Ϫ, 127.7Ϫ, 71.3Ϫ, 68.3Ϫ, 51.3Ϫ, 48.8Ϫ, 44.4ϩ,
38.8ϩ, 36.7ϩ, 35.5ϩ, 35.2Ϫ, 33.0ϩ, 29.7Ϫ, 24.0ϩ, 22.6Ϫ,
Ϫ2.5Ϫ and Ϫ3.7Ϫ; C: Rf(EtOAc–light petroleum, 7 : 3) 0.22;
νmax(CDCl3)/cmϪ1 3689 (OH), 3608 (OH), 1793, 1250 (SiMe),
1216, 1166 (SiPh), 1095 and 922; δH(500 MHz, CDCl3) 7.51–7.46
(2 H, m, m-Ph), 7.36–7.31 (3 H, m, o,p-Ph), 3.84 (1 H, dt, J 11.0
and 4.2, SiCHCHCHOH), 3.41 (1 H, tt, J 10.6 and 4.4, CHCH-
CH2CHOH), 2.00–1.85 (2 H, 2 m’s, CHCHCHAHBCHO and
CH2CHAHBCHO), 1.79–0.93 (14 H, MeCHCH2, CH2CH-
(Si)CHCHCHAHB and CH2CH2CHAHBCHO), 0.89 (3 H, d,
J 6.4, MeCH), 0.33 (3 H, s, SiMeAMeB) and 0.31 (3 H, s, SiMeA-
MeB); δC(125 MHz, CDCl3) 139.2ϩ, 133.7Ϫ, 128.9Ϫ, 127.7Ϫ,
71.8Ϫ, 70.8Ϫ, 44.5Ϫ, 42.6ϩ, 39.8ϩ, 35.4Ϫ, 35.3ϩ, 31.7ϩ,
30.7ϩ, 29.6Ϫ, 24.0ϩ, 23.2Ϫ, 22.4Ϫ, Ϫ2.1Ϫ and Ϫ2.7Ϫ; m/z
(ESI) 369 (100%, Mϩ ϩ Naϩ)(Found: Mϩ ϩ Na, 369.2219.
C21H34O2Si requires M ϩ Na, 346.2328).
oxide (NMO) (10 mg, 54 µmol) and molecular sieves (4 Å)
(10 mg) were stirred in dichloromethane (1.0 cm3) under argon
at room temperature for 1 h. The mixture was filtered through a
pad of silica and Celite, and the pad washed with dichloro-
methane (4 × 3 cm3). The filtrate was evaporated under reduced
pressure and the residue was chromatographed (SiO2, EtOAc–
light petroleum, 2 : 8) to give the ketone 36 (12 mg, 62%) as
needles; mp 160–162 ЊC (from hexane–CH2Cl2); Rf(EtOAc–
light petroleum, 3 : 7) 0.25; νmax(CDCl3)/cmϪ1 1727, 1708 (CO),
1638 (CO), 1620 (CO), 1548 (NO2), 1381, 1345 (NO2), 1283
(SiMe), 1215 and 1171 (SiPh); δH(500 MHz, CDCl3) 9.25 (1 H,
t, J 2.1, p-(NO2)2C6H3), 9.03 (2 H, d, J 2.1, 2 × o-(NO2)2C6H3),
7.50 (2 H, d, J 6.9, 2 × m-Ph), 7.29 (3 H, t, J 7.4, 2 × o- and 1 ×
p-Ph), 4.31–4.29 (1 H, m, CHOCO), 2.43–2.36 (2 H, m, CHA-
HBCO, CHCO), 2.30–2.01 (5 H, m, MeCHCHAHBCHSi,
CHAHBCO and CHAHBCHCHAHBCHO), 1.98–1.93 (1 H, m,
CHCHCO), 1.79–1.69 (2 H, m, CHSi and CHAHBCHA-
HBCHO), 1.65–1.56 (1 H, m, MeCHCHAHBCHSi), 1.41–1.32
(1 H, m, CHAHBCHO), 1.29–1.15 (2 H, m, CHAHBCHCHA-
HBCHO and CHAHBCHAHBCHO), 1.03 (3 H, d, J 5.8, Me),
0.93–0.79 (2 H, m, CHAHBCHAHBCHAHBCHO), 0.39 (3 H, s,
SiMeAMeB) and 0.31 (3 H, s, SiMeAMeB); δC(125 MHz, CDCl3)
211.4ϩ, 161.4ϩ, 148.6ϩ, 139.5ϩ, 134.6ϩ, 133.6Ϫ, 129.3Ϫ,
128.9Ϫ, 127.8Ϫ, 122.1Ϫ, 76.3Ϫ, 59.3Ϫ, 51.6ϩ, 35.6ϩ, 34.6Ϫ.
34.5Ϫ, 31.5ϩ, 30.9ϩ, 29.7ϩ, 28.2Ϫ, 23.4ϩ, 22.5Ϫ, Ϫ1.5Ϫ and
Ϫ1.9Ϫ; m/z (ESI) 561 (100%, Mϩ ϩ Naϩ)(Found: Mϩ ϩ Na,
561.2035. C28H34O7N2Si requires M ϩ Na, 561.2033).
Crystal data for 36. C28H34N2O7Si, M = 538.66, ortho-
rhombic, space group P212121 (no. 19), a = 7.5858(1), b =
8.4440(1), c = 43.4801(7) Å, U = 2785.10(7) Å3, Z = 4, µ(Mo–
Kα) = 0.132 mmϪ1, 10681 reflections measured at 180(2) K
using an Oxford Cryosystems Cryostream cooling apparatus,
3281 unique (Rint = 0.074); R1 = 0.042, wR2 = 0.078 [I>2σ(I )].
The structure was solved with SHELXS-97 and refined with
SHELXL-9.31 CCDC reference numbers 212800–212802. See
graphic data in .cif or other electronic format.
(3R,5R)-5-(Dimethylphenylsilyl)-3-methyl-6-(5Ј-oxohexyl-
idene)-1-trimethylsilyloxycyclohexene 34
(1S,2S,3R,5S,1ЈS,3ЈR)-3-Dimethyl(phenyl)silyl-2-(3Ј-3,5-di-
nitrobenzoyloxyclohexyl)-5-methylcyclohexan-1-ol
n-Butyllithium (1.40 mol dmϪ3 solution in hexane, 0.08 cm3,
0.112 mmol) was added to a solution of freshly distilled diiso-
propylamine (16 µl, 0.01 mmol) at 0 ЊC and the mixture stirred
for 20 min, and cooled to Ϫ78 ЊC. The ketone 33 (35 mg, 0.10
mmol) in THF (0.5 cm3) was added dropwise and the mix-
ture stirred at that temperature for 1 h. Chlorotrimethylsilane
(0.03 cm3, 0.20 mmol) was added slowly and the mixture stirred
for 1 h, during which time it was warmed to room temperature.
The mixture was quenched with saturated sodium hydro-
gencarbonate (5 cm3) and extracted with ether (3 × 5 cm3). The
combined extracts were washed with brine, dried (MgSO4), and
evaporated under reduced pressure. The residue was chromato-
graphed (SiO2, EtOAc–light petroleum, 1 : 99 to 2 : 98) to give
the silyl enol ether 34 (6 mg, 15%); Rf(EtOAc–light petroleum,
The diol A (10 mg, 0.03 mmol), 3,5-dinitrobenzoyl chloride (33
mg, 0.14 mmol), pyridine (0.5 cm3) and DMAP (5 mg, 0.03
mmol) were stirred in dichloromethane (1 cm3) at room temper-
ature for 1 h, during which time a white solid precipitated. The
mixture was quenched with water (5 cm3) and extracted with
ether (3 × 5 cm3). The combined organic layers were washed with
brine (5 cm3), dried (MgSO4) and evaporated under reduced pres-
sure. The residue was chromatographed (SiO2, EtOAc–light pet-
roleum, 5 : 95) to give the mono ester (16 mg, 99%); Rf(EtOAc–
light petroleum, 2 : 8) 0.3; νmax(solution cell, CDCl3)/cmϪ1 3473
(OH), 1726 (CO), 1627, 1601, 1213 (SiMe), 1045 and 928; δH(400
MHz, CDCl3) 9.22 (1 H, t, J 2.1, p-(NO2)2C6H3), 9.14 [2 H, d,
J 2.2, 2 × o-(NO2)2C6H3], 7.60 (2 H, m, 2 × m-Ph), 7.30 (3 H, m,
2 × o- and 1 × p-Ph), 4.60 (1 H, tt, J 8.9 and 4.3, CHOCO), 4.11
(1 H, br s, CHOH ), 2.29–0.81 (16 H, series of ms, CHCH-
(Si)CH2CH(Me)CH2 and CH2CHCH2CH2CH2), 0.80 (3 H, d,
J 6.5, MeCH), 0.47 (3 H, s, SiMeAMeB) and 0.41 (3 H, s, SiMeA-
MeB); δC(125 MHz, CDCl3) 161.7ϩ, 148.6ϩ. 141.6ϩ, 134.7ϩ,
133.8Ϫ, 129.3Ϫ, 128.6Ϫ, 127.6Ϫ, 122.1Ϫ, 76.7Ϫ, 66.2Ϫ, 51.4Ϫ,
42.9ϩ, 37.3ϩ, 35.8Ϫ, 31.5ϩ29.6ϩ, 29.3ϩ, 24.0Ϫ, 23.7Ϫ, 23.5ϩ,
22.3Ϫ, Ϫ0.2Ϫ and Ϫ0.5Ϫ.
2 : 8) 0.6; νmax(CDCl3)/cmϪ1 1708 (CO), 1639 (C᎐C), 1602, 1297,
᎐
1261 (SiMe), 1216, 1166 (SiPh), 1095 and 746; δH(400 MHz,
CDCl3) 7.52–7.32 (5 H, m, Ph), 5.60 (1 H, dd, J 8.8 and 5.2,
CH᎐CCOTMS), 4.75 (1 H, br s, CH᎐COTMS), 2.42 (1 H, dd,
᎐
᎐
J 5.0 and 2.2, CHSi), 2.41–2.34 (1 H, m, MeCH ), 2.22 (2 H, dt,
J 7.2 and 6.8, CH2COMe), 1.89–1.82 (1 H, dd, J 4.8 and 2.8,
CH CH CHSi), 1.82–1.73 (1 H, m, CH CH CH᎐C), 1.50–
᎐
A
B
A
B
1.41 (3 H, m, CH CH CH᎐C and CH CH CH CH᎐C), 1.32
᎐
᎐
A
B
2
A
B
(1 H, ddd, J 24.2, 11.8 and 5.2, CHACHBCHSi), 0.91 (3 H, d,
J 6.8, MeCH), 0.32 (3 H, s, SiMeAMeB), 0.28 (3 H, s, SiMeA-
MeB) and 0.21 (9 H, s, SiMe2); δC(125 MHz, CDCl3) 209.1ϩ,
148.0ϩ, 139.0ϩ, 133.8Ϫ, 133.5ϩ, 128.8Ϫ, 127.6Ϫ, 121.5Ϫ,
113.8Ϫ, 43.1ϩ, 34.2ϩ, 29.8Ϫ, 29.1Ϫ, 27.2ϩ, 26.9Ϫ, 23.8ϩ,
(2S,3R,5S,1ЈS,3ЈR)-3-Dimethyl(phenyl)silyl-2-(3Ј-3,5-dinitro-
benzoyloxyclohexyl)-5-methylcyclohexanone 36
The mono ester (16 mg, 36 µmol), tetrapropylammonium per-
ruthenate (TPAP) (13 mg, 36 µmol), N-methylmorpholine-N-
229Ϫ, 0.9Ϫ, Ϫ2.6Ϫ and Ϫ3.1Ϫ; m/z (ESI) 437 (100%, Mϩ
ϩ
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 3 9 8 9 – 4 0 0 4
4002