ELEUTHESIDES AND THEIR ANALOGS: VII.
1507
Rf 0.35 (petroleum ether–ethyl acetate, 3:1), [α]D20
=
207.04 (C8). Mass spectrum: m/z 266.2 [M]+.
C14H18O5. Calculated: M 266.1154.
–15.5° (c = 1.0, CHCl3). The ratio IV/V was 1:3
according to the 1H NMR data.
Acetates VII–IX. A solution of 0.300 g
(1.13 mmol) of acetate mixture IV–VI in 10 mL of
methylene chloride was cooled to 0°C, 0.41 mL
(1.69 mmol) of 1,2-bis(trimethylsiloxy)ethane and
0.006 mL (0.034 mmol) of trimethylsilyl trifluoro-
methanesulfonate were added, and the mixture was
stirred for 5 h at room temperature. The mixture was
neutralized with a saturated solution of sodium hydro-
gen carbonate, the aqueous phase was extracted with
ethyl acetate (3×30 mL), the extract was dried over
MgSO4, the solvent was distilled off on a rotary evap-
orator, and the residue was subjected to chromatog-
raphy on silica gel to isolate 0.321 g (92%) of an oily
mixture of acetates VII–IX.
1
Compound IV. H NMR spectrum (C6D6), δ, ppm:
0.65 d (3H, CH3, 3JMe,3 = 7.1 Hz), 1.45 d.d (1H, 2-H,
3
3J2,3 = 7.3, J2,7 = 6.6 Hz), 1.56 s (3H, OAc), 2.35 m
3
(1H, 3-H), 2.92 d (1H, 7-H, J7,2 = 6.6 Hz), 3.13 m
2
(1H, 6-H), 3.49 d.d (1H, 11-endo-H, J = 7.6,
3J11-endo,1 = 5.1 Hz), 3.57 d (1H, 11-exo-H, 2J = 7.6 Hz),
2
3
3.67 d.d (1H, 13-HA, J = 10.9, J13A, 6 = 4.8 Hz),
3.78 d.d (1H, 13-HB, 2J = 10.9, 3J13B,6 = 8.4 Hz), 3.99 d
(1H, 1-H, 3J1,11-endo = 5.1 Hz), 5.20 s (1H, 9-H), 5.32 m
(2H, 4-H, 5-H). 13C NMR spectrum (C6D6), δC, ppm:
19.42 (CH3), 19.98 (OAc), 27.91 (C3), 30.63 (C6),
40.99 (C7), 45.77 (C2), 65.65 (C13), 66.81 (C11), 74.59
(C1), 101.71 (C9), 122.98 (C4), 133.82 (C5), 170.04
(MeC=O), 200.23 (C8). Mass spectrum: m/z 266.2
[M]+. C14H18O5. Calculated: M 266.1154.
(1′S,2′S,3′S,6′S,7′R,9′R)-{3′-Methyl-10′,12′-di-
oxaspiro[1,3-dioxolane-2,8′-tricyclo[7.2.1.02,7]dodec-
4′-en]-6′-yl}methyl acetate (VII). Rf 0.29 (petroleum
1
Compound V. H NMR spectrum (C6D6), δ, ppm:
1
1.03 d (3H, CH3, 3JMe,6 = 6.8 Hz), 1.70 d.d.d (1H, 2-H,
3J2,7 = 11.6, 3J2,3 = 4.8, 3J2,1 = 1.4 Hz), 2.12 s (3H, Ac),
2.48 m (1H, 3-H), 2.62 m (1H, 6-H), 2.72 d.d (1H,
ether–ethyl acetate, 2:1). H NMR spectrum, δ, ppm:
1.06 d (3H, CH3, J = 7.1 Hz), 1.40 m (1H, 2-H), 2.06 s
(3H, Ac), 2.37 d (1H, 7-H, 3J7,2 = 5.8 Hz), 2.43 m (1H,
CH), 2.63 m (1H, CH), 3.80–4.10 m (8H, CH2O),
3
3
7-H, J7,2 = 11.5, J7,6 = 10.0 Hz), 3.62 m (2H, 11-H),
3
4.61 d (1H, 1-H, J1,11 = 4.5 Hz), 5.00 s (2H, 9-H),
3.73 m (1H, 13-HB), 3.84 m (1H, 13-HA), 4.60 d.d (1H,
3
5.52 m (1H, 5-H, J = 10.0, 6.8, 3.1 Hz), 5.67 m (1H,
4-H). 13C NMR spectrum, δC, ppm: 19.47, 20.43,
27.85, 33.48, 35.15, 41.62, 60.16, 65.76, 66.15, 67.38,
73.82, 100.36, 108.65, 126.01, 132.02, 170.56.
1-H, J1,11-endo = 3.6 Hz), 5.17 s (1H, 9-H), 5.60 d (1H,
5-H, 3J5,4 = 10.2 Hz), 5.90 d.d.d (1H, 4-H, 3J4,5 = 10.2,
3J4,3 = 5.6, J4,6 = 2.2 Hz). 13C NMR spectrum (C6D6),
4
δC, ppm: 19.98, 20.38, 24.59, 33.54, 39.59, 44.38,
65.65, 66.74, 74.80, 101.61, 124.76, 131.72, 170.04,
200.23. Mass spectrum: m/z 266.2 [M]+. C14H18O5.
Calculated: M 266.1154.
(1′S,2′S,3′S,6′R,7′S,9′R)-{3′-Methyl-10′,12′-di-
oxaspiro[1,3-dioxolane-2,8′-tricyclo[7.2.1.02,7]dodec-
1
4′-en]-6′-yl}methyl acetate (VIII). H NMR spec-
trum, δ, ppm: 1.08 d (3H, CH3, J = 6.9 Hz), 1.62–
1.78 m (2H, CH), 2.02 s (3H, Ac), 2.42 m (1H, CH),
2.66 m (1H, CH), 3.59 d (1H, 11-H, J = 7.0 Hz),
3.69 m (1H, 11-H), 3.80–4.10 m (6H, CH2O), 4.60 d
(1H, 1-H, J = 4.6 Hz), 5.04 s (1H, 9-H), 5.52 m (1H,
5-H, J = 9.8, 1.2 Hz), 5.77 d.d.d (1H, 4-H, J = 9.8, 5.5,
2.3 Hz). 13C NMR spectrum, δC, ppm: 20.85, 21.08,
30.27, 33.03, 36.23, 41.16, 64.68, 65.76, 65.90, 71.04,
73.47, 101.93, 108.49, 127.80, 132.81, 170.69.
(1S,2S,3S,6R,7S,9R)-(6-Methyl-8-oxo-10,12-di-
oxatricyclo[7.2.1.02,7]dodec-4-en-3-yl)methyl acetate
(VI). Oily material, Rf 0.33 (petroleum ether–ethyl
acetate, 3:1), [α]D20 = +54.9° (c = 1.0, CHCl3). H NMR
1
3
spectrum, δ, ppm: 1.14 d (3H, CH33, JMe,6 = 6.6 Hz),
3
3
1.83 d.d.d (1H, 2-H, J2,7 = 11.5, J2,3 = 4.0, J2,1
=
=
3
1.3 Hz), 2.11 s (3H, Ac), 2.37 d.d (1H, 7-H, J7,2
3
11.5, J7,6 = 11.5 Hz), 2.45 m (1H, 6-H), 2.72 m (1H,
3-H), 3.62 d (1H, 11-exo-H, 2J = 7.1 Hz), 3.82 d.d (1H,
2
3
11-endo-H, J = 7.1, J11-endo,1 = 5.2 Hz), 4.18 d.d (1H,
(1′S,2′S,3′S,6′R,7′S,9′R)-{6′-Methyl-10′,12′-di-
2
3
13-HB, J = 11.7, J13B,3 = 4.9 Hz), 4.42 d.d (1H,
oxaspiro[1,3-dioxolane-2,8′-tricyclo[7.2.1.02,7]dodec-
2
3
1
13-HA, J = 11.7, J13A,3 = 6.8 Hz), 4.90 d.d (1H, 1-H,
4′-en]-3′-yl}methyl acetate (IX). H NMR spectrum,
3J1,11-endo = 5.2, J1,2 = 1.3 Hz), 5.15 s (1H, 9-H),
δ, ppm: 1.02 d (3H, CH3, J = 7.0 Hz), 1.65 d.d.d (1H,
2-H, J = 12.5, 4.9, 2.1 Hz), 1.73 d.d (1H, 7-H, J =
12.5, 10.0 Hz), 2.08 s (3H, Ac), 2.28 m (1H, CH),
2.52 m (1H, CH), 3.62 d (1H, 11-H, J = 7.0 Hz),
3.70 m (1H, 11-H), 3.81–3.95 m (2H, CH2), 3.96–
4.12 m (4H, CH2, 13-H), 4.35 d.d (1H, 1-H, J = 4.5,
2.1 Hz), 5.04 s (1H, 9-H), 5.53 m (1H, 5-H, J = 9.8,
3
3
3
5.60 d.d (1H, 5-H, J5,4 = 9.7, J5,6 = 1.0 Hz),
3
3
4
5.67 d.d.d (1H, 4-H, J4,5 = 9.7, J4,3 = 5.0, J4,6
=
1.7 Hz). 13C NMR spectrum, δC, ppm: 20.82 (CH3),
21.01 (CH3CO), 31.54 (C6), 38.05 (C3), 41.18 (C2),
43.07 (C7), 63.97 (C13), 71.15 (C11), 73.61 (C1), 99.09
(C9), 125.19 (C4), 135.74 (C5), 170.76 (CH3C=O),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 10 2014