A NOVEL APPROACH TO KEY SYNTHONS
39
5H, Ph). 13C NMR (δ, ppm): 20.65 (CH3), 22.03 (CH3),
22.18 (CH3), 22.29 (C-3), 25.45 (CH3), 27.61 (CMe2),
30.60 (C-2), 36.65 (C-1'), 40.28 (C-4), 43.35 (C-5),
48.03 (C-8), 54.71 (OMe), 72.02 (OCH2Ph), 83.29 (C-
2'), 86.22 (C-1), 109.22 (C-6), 127.84, 127.95, 128.02,
128.20, 128.37, 137.57 (Ph), 204.32 (C=O).
(1R,3S,6S,7R,10S)-7-Isopropyl-4,10-dimethylbi-
cyclo[4.4.0]dec-4-ene-3,10-diol (7), mp 102–103°C,
[α ]2D6 +49.1° (c 1.0, CHCl3). 1H NMR (δ, ppm, J, Hz):
0.81 (d, 3H, CH3, J = 7.0), 0.88 (d, 3H, CH3, J = 7.0),
1.20 (m, 1H, Hax-9), 1.25 (s, 3H, CH3), 1.37 (m, 1H,
H-7), 1.50 (m, 3H, CH2-8, Heq-9), 1.67 (dd, 1H, Heq-2,
For C23H34O4 anal. calcd. (%): C, 73.76; H, 9.15.
Found (%): C, 73.53; H, 9.24.
eq
2–3
eq
2–1
Jgem = 9.5, J
= 5.0, J
not determined), 1.73 (m,
1H, H-1), 1.75 (s, 3H, CH3), 1.88 (dqq, 1H, Me2CH,
(1R,2R,3R,6S,8S)-8-Acetyl-3-isopropyl-6-methyl-
2-dimethoxymethyl-7-oxabicyclo[4.3.0]nonane (9),
JMe CH-7 = 4.5, JMe CH–Me = 7.0), 2.05 (m, 1H, H-6,
2
2
oil, [α ]2D6 +19.4° (c 1.0, CHCl3). H NMR (δ, ppm,
1
ax
2–3
J
6−5 = 5.0), 2.24 (dd, 1H, Hax-2, Jgem = 9.5, J
= 7.5),
J, Hz): 0.72 (d, 3H, CH3, J = 7.0), 0.83 (d, 3H, CH3, J =
7.0), 1.08–1.20 (m, 3H, CH), 1.25 (s, 3H, CH3), 1.38
(m, 1H, CH), 1.43–1.58 (m, 3H, CH), 1.78 (m, 2H,
CH2), 2.12 (s, 3H, CH3), 2.20 (m, 1H, CH), 3.33 (s, 6H,
OCH3), 4.23 (d, 1H, CH(OMe)2, J = 3.5), 4.35 (m, 1H,
H-8). 13C NMR (δ, ppm): 15.14 (CH3), 21.55 (CH3),
21.81 (C-4), 24.55 (CH3), 26.18 (CH3), 26.23 (CMe2),
32.06 (C-9), 34.55 (C-5), 37.47 (C-1), 39.95 (C-2),
44.34 (C-3), 56.08 (OCH3), 56.47 (OCH3), 82.61 (C-8),
83.48 (C-6), 107.09 (C(OMe)2), 210.94 (C=O).
2.30 (br s, 1H, OH), 2.56 (br s, 1H, OH), 4.03 (dd, 1H,
eq
ax
H-3, J = 5.0, J
= 7.5), 5.54 (qd, 1H, H-5, J5-Me =
3–2
3–2
1.5, J5–6 = 5.0). 13C NMR (δ, ppm): 16.22 (CH3), 19.62
(CH3), 21.15 (C-8), 21.70 (CH3), 26.47 (Me2C), 27.74
(CH3), 29.80 (C-2), 35.13 (C-9), 37.18 (C-6), 43.32
(C-7), 44.40 (C-1), 70.72 (C-3), 72.07 (C-10), 128.37
(C-5), 137.29 (C-4).
For C15H6O2 anal. calcd. (%): C, 75.58; H, 10.99.
Found (%): C, 75.78; H, 11.19.
For C17H30O4 anal. calcd. (%): C, 68.45; H, 10.07.
Found (%): C, 68.74; H, 9.81.
MS (EI) (m/z (Irel, %): 298 [M]+ (37).
(1R,3S,6S,7R,10S)-3-Benzyloxy-7-isopropyl-4,10-
dimethylbicyclo[4.4.0]dec-4-en-10-ol (7a), mp 97–
99°C, [α ]2D2 +54.6° (c 1.0, CHCl3). 1H NMR (δ, ppm,
[1R,2R,3R,6S,8S,(2'R)]-8-(2'-Hydroxybut-3'-yn-
2'-yl)-3-isopropyl-6-methyl-2-dimethoxymethyl-7-oxa-
bicyclo[4.3.0]nonane (10a). 1H NMR (δ, ppm, J, Hz):
0.78 (d, 3H, CH3, J = 6.7), 0.92 (d, 3H, CH3, J = 6.7),
J, Hz): 0.82 (d, 3H, CH3, J = 6.9), 0.90 (d, 3H, CH3, J =
6.9), 1.15 (ddd, 1H, H-8, J = 3.4, J = 4.0, and J = 11.2),
1.28 (s, 3H, CH3), 1.48 (m, 1H, H-7, J = 3.0), 1.50 (m,
3H, CH2-9, H-8), 1.68 (m, 1H, H-1), 1.78 (s, 3H, CH3),
1.98 (dqq, 1H, Me2CH, J = 3.0, J = 6.9), 2.05 (m, 1H,
H-6), 2.30 (m, 1H, H-2, J = 10.0), 2.46 (ddd, 1H, H-2,
J = 1.0, J = 6.3, J = 10.0), 3.96 (dd, 1H, H-3, J = 6.3,
J = 8.4), 4.51 (d, 1H, OCH2Ph, J = 11.5), 4.70 (dd, 1H,
OCH2Ph, J = 11.5, J = 10.4), 5.67 (d, 1H, H-5, J = 5.4),
7.38 (m, 5H, Ph). 13C NMR (δ, ppm): 15.24 (CH3),
19.76 (CH3), 21.32 (C-8), 21.46 (CH3), 24.80 (C-2),
26.32 (CH3), 27.68 (CMe2), 35.06 (C-9), 36.88 (C-6),
43.68 (C-7), 44.10 (C-1), 70.42 (OCH2Ph), 71.83
(C-10), 78.22 (C-3), 128.80 (C-5), 135.48 (C-4),
127.35, 127.66, 128.33, 138.69 (Ph).
0.95 (m, 1H, Hax-4), 1.28 (s, 3H, CH3), 1.40 (s, 3H,
CH3), 1.50–1.62 (m, 4H, H-2, CH2-5, Heq-4), 1.80–1.93
(m, 4H, Me2CH, CH2-9, H-1), 2.22 (dddd, 1H, H-3,
eq
3–4
ax
3–4
J
= 6.4, J3-Me CH = 6.4, J
= 12.0, J3–2 = 12.0),
2
4.03 (dd, 1H, H-8, Ja8–9 = 5.4, J8b–9 = 10.5), 4.30 (d,
CH(OMe)2, J(MeO) CH-2 = 3.6). 13C NMR (δ, ppm):
2
15.75 (CH3), 21.67 (CH3), 21.84 (C-4), 25.0 (CH3),
26.46 (CMe2), 29.35 (C-9), 35.89 (C-5), 37.90 (C-3),
39.98 (C-2), 44.46 (C-1), 56.05 (OCH3), 56.25 (OCH3),
67.69 (HC≡), 71.03 (C-6), 82.32 (COH), 84.55 (C-8),
86.93 (C≡), 107.53 (C(OMe)2).
[1R,2S,3R,6S,8S(2'R)]-8-(2'-Hydroxybut-3'-yn-2'-
yl)-3-isopropyl-6-methyl-2-(2''-cyano-2''-ethoxy-
carbonylethenyl)-7-oxabicyclo[4.3.0]nonane (11),
[α ]2D0 +50.6° (c 1.0, CHCl3). 1H NMR (δ, ppm, J, Hz):
0.78 (d, 3H, CH3, J = 6.8), 0.92 (d, 3H, CH3, J = 6.8),
For C22H32O2 anal. calcd. (%): C, 80.44; H, 9.82.
Found (%): C, 80.79; H, 9.60.
[1S,4R,5R,6S,8R(2'S)]-8-(2'-Benzyloxy-3'-oxobu-
tyl)-4-isopropyl-1-methyl-6-methoxy-7-oxabicyclo-
[3.2.1]octane (8), oil, [α ]2D0 –55.0° (c, 1.0, CHCl3). 1H
NMR (δ, ppm, J, Hz): 0.80 (d, 3H, CH3, J = 6.8), 0.87
(d, 3H, CH3, J = 6.8), 1.18 (s, 3H, CH3), 1.25 (m, 1H,
H-4), 1.35–1.45 (m, 3H, CH2-2 and H-8), 1.50–1.62
(m, 3H, Me2CH, CH2-3), 1.75 (ddd, 1H, CH2-1', J =
2.6, J = 9.6, and J = 11.0), 2.05 (ddd, 1H, CH2-1', J =
3.8, J = 9.9, and J = 11), 2.12 (s, 3H, CH3), 2.40 (d, 1H,
H-5, J = 3.4), 3.30 (s, 3H, OCH3), 3.92 (dd, 1H, H-2',
J = 2.6, J = 9.9), 4.30 (d, 1H, OCH2Ph, J = 10.8), 4.53
(d, 1H, OCH2Ph, J = 10.8), 4.70 (s, 1H, H-6), 7.30 (m,
1.10 (m, 1H, Hax-4), 1.30 (m, 1H, Heq-4), 1.39 (t, 3H,
CH3CH2O, J = 7.2), 1.44 (s, 6H, CH3), 1.55–1.76 (m,
4H, CH2-5, Me2CH, H-3), 2.10 (m, 3H, CH2-9, H-1),
2.50 (s, 1H, ≡CH), 2.60 (br s, 1H, OH), 3.0 (ddd, 1H,
H-2, J2–1 = 4.5, J2-CH= = 11.0, J2–3 = 11.0), 4.02 (dd,
1H, H-8, Ja8–9 = 5.8, J8b–9 = 10.3), 4.33 (q, 2H, OCH2,
JCH –Me = 6.1), 7.51 (d, 1H, CH=, J=CH-2 = 11.0). 13C
2
DOKLADY CHEMISTRY Vol. 382 Nos. 4–6 2002