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PERLMUTTER AND ROSE
NMR (200 mHz, CDCl3) d 0.99 (s, 3H,CH3), 1.18 (s, 3H, CH3), 1.40 (m, 2H, CH2), 1.60
(m, 2H, CH2), 1.80–2.20 (m, 8H, 3ꢀCH2, CH and OH), 3.33 (pent, 1H, J =4.1 Hz, H-2),
3.49 and 3.56 (AB quartet, 2H, J =13.8 Hz, CH2SO2), 3.95 (t, 1H, J = 6.3 Hz, CHN), 4.65
(m, 1H, H-1), 4.90 (m, 2H, CH = CH2), 5.70 (m, 1H, CH = CH2), 6.25 (dd, 1H, J = 5.8,
16.0 Hz, CH = CHPh), 6.68 (d, 1H, J =16.0 Hz, CH = CHPh), 7.20–7.50 (m, 5H, Ph). 13
C
NMR (75 mHz, CDCl3) d 19.6(C-80), 20.9(C-90), 26.4(C-50), 27.5(C-3), 31.3(C-4), 33.0(C-
60), 38.6(C-30), 44.7(C-40), 47.8(C-70), 48.2(C-10), 50.1(C-2), 53.2(C-100), 65.4(C-20),
71.9(C-1), 115.0(CH2 = C), 126.5(Ph), 127.4(CH = C), 128.3(Ph), 128.5(Ph),
131.2(CH = C), 136.6(Ph), 137.5(CHC), 174.9(CO). Exact mass m/z calcd for
C25H32NSO3 (MꢁOH) 426.2103, found 426.2083.
(2R)-N-[(1R,2S)-2-Hydroxy-3-cyclopenten-1-oyl]bornane-10,2-sultam (6). The
aldol adduct 4 (680 mg, 1.6 mmol) was dissolved in degassed dichloromethane (60 mL)
under argon. A solution of Grubbs’ catalyst (130 mg, 0.16 mmol) in dichloromethane (5
mL) was added and the reaction stirred overnight. Evaporation of the solvent, followed
by chromatography (hexane/ethyl acetate, 2:1), gave 6 (415 mg, 83%) as colorless
crystals, mp 141–143 °C. [a]D25 + 13 °C (c 1.0, CH2Cl2). Rf (0.13) in hexane/ethyl
acetate (4:1). IR (nujol/CH2Cl2): 3514, 2924, 2854,1686, 1458, 1378, 1360, 1321, 1274,
1249, 1208, 1166, 1134, 1119, 1059, 1040, 1001, 964, 802, 788, 721 cmꢁ1. 1H NMR (200
mHz, CDCl3) d 0.98 (s, 3H,CH3), 1.17 (s, 3H,CH3), 1.30–1.45 (m, 2H, CH2), 1.70–2.10
(m, 8H, 3ꢀCH2, CH and OH), 2.55 (m, 1H, H-5), 2.90 (m, 1H, H-5), 3.51 and 3.53 (AB
quartet, 2H, J =13.9 Hz, CH2SO2), 3.85 (m, 1H, H-1), 3.96 (dd, 1H, J =5.3, 5.3 Hz,
CHN), 5.20 (m, 1H, H-2), 5.75 (m, 1H, H-4), 5.95 (m, 1H, H-3). 13C NMR (50 mHz,
CDCl3) d 20.0(C-80), 21.1(C-90), 26.5(C-50), 32.9(C-60), 36.0(C-5), 38.8(C-30), 44.7(C-
40), 47.1(C-1), 47.9(C-70), 48.4(C-10), 53.3(C-100), 65.7(C-20), 78.2(C-2), 131.7(C-4),
133.7(C-3), 171.7(CO). Exact mass m/z Calcd for C16H23NSO4Na (M +Na+) 348.1245,
found 348.1231.
(2R)-N-[(1R,2S)-2-Hydroxy-3-cyclohexen-1-oyl]bornane-10,2-sultam (7). The
aldol adduct 5 (690 mg, 1.5 mmol) was dissolved in degassed dichloromethane (55 mL)
under argon. A solution of Grubbs’ catalyst (125 mg, 0.15 mmol) in dichloromethane (10
mL) was added and the reaction stirred overnight. Evaporation of the solvent, followed
by chromatography (hexane/ethyl acetate, 2:1), gave 7 (393 mg, 74%) as colorless
25
crystals, mp 176–178 °C. [a]D ꢁ 58 °C (c 1.6, CH2Cl2). Rf (0.25) in hexane/ethyl
acetate (4:1). IR (nujol/CH2Cl2): 3424, 2924, 2854, 1689, 1665, 1461, 1377, 1330, 1264,
1237, 1213, 1166, 1131, 1051, 1000, 939, 829, 743 cmꢁ1. 1H NMR (200 mHz, CDCl3) d
0.98 (s, 3H, CH3), 1.16 (s, 3H, CH3), 1.20–1.60 (m, 5H, 2ꢀCH2 and CH), 1.70–2.20 (m,
7H, 3ꢀCH2, and OH), 3.10 (m, 1H, H-1), 3.49 and 3.50 (AB quartet, 2H, J = 13.9 Hz,
CH2SO2), 3.92 (t, 1H, J = 6.0 Hz, CHN), 4.45 (m, 1H, H-2), 5.89 (m, 2H, H-3 and H-4).
13C NMR (50 mHz, CDCl3) d 19.8(C-80), 20.7(C-90), 21.4(C-5), 25.4(C-6), 26.4(C-50),
32.7(C-60), 38.4(C-30), 44.5(C-40), 44.9(C-1), 47.8(C-70), 48.4(C-10), 53.0(C-100), 63.1(C-
2), 64.9(C-20), 127.1(C-4), 130.9(C-3), 176.3(CO). [M + 1] m/z 340.2 (100%),
[M+ 1ꢁH2O] m/z 322.2 (65%).
Anal. Calcd for C17H25NSO4: C, 60.15; H, 7.42; N, 4.13: Found: C, 59.90; H, 7.62;
N, 4.12.
(2R)-N-[(1R,2S,3R,4R)-2,3,4-Trihydroxycyclopentan-1-oyl]bornane-10,2-sul-
tam (9). A solution of 6 (180 mg, 0.57 mmol) in t-butyl alcohol (3 mL) and DMF (3