Russian Journal of Organic Chemistry, Vol. 37, No. 11, 2001, pp. 1666 1667. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 11, 2001,
pp. 1736 1737.
Original Russian Text Copyright
2001 by Tsypysheva, Kunakova, Spirikhin, Valeev, Tolstikov.
SHORT
COMMUNICATIONS
Ozonolytic Hydroxylation of 3-Benzyloxy-(+)- -Cadinol*
I. P. Tsypysheva1, A. M. Kunakova1, L. V. Spirikhin1,
F. A. Valeev2, and G. A. Tolstikov2
1
Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
fax: (3472)356066; e-mail:chemorg@anrb.ru
2
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
Received August 8, 2001
While developing approaches to formation of the
4,7-oxaeunicellane nucleus (which is a central frag-
ment of eleuthesides [1]) on the basis of (+)- -cadinol
(I), we performed ozonolysis of its 3-benzyloxy
derivative II in CH2Cl2 at 78 C, followed by treat-
ment with Me2S. As a result, anomalous ketotriol
III was obtained.
of the double bond in II is a formal result of stereo-
specific intramolecular aldol condensation of inter-
mediate A.
The NMR spectra were recorded on a Bruker AM-
300 instrument at 300.13 MHz (1H) and 75.47 MHz
(13C). The signals were assigned on the basis of the
CH correlation spectra. The optical rotations were
measured on a Perkin Elmer 141 polarimeter. We
used (+)- -cadinol with mp 137.8 C, [ ]2D0 = +100.3
(c = 1.0, CHCl3). 3-Benzyloxy derivative II was syn-
thesized by the action of SeO2 AcO2 on (+)- -cadinol
(I) and subsequent benzylation.
(1R,3S,6S,7R,10S)-3-Benzyloxy-7-isopropyl-4,10-
dimethylbicyclo[4.4.0]dec-4-en-10-ol (II). mp 97
99 C, [ ]2D2 = +54.6 , c = 1.0, CHCl3). 1H NMR spec-
trum, , ppm: 0.82 d (3H, CH3, J = 6.9 Hz), 0.90 d
(3H, CH3, J = 6.9 Hz), 1.15 d.d.d (1H, 8-H, J = 3.4,
4.0, 11.2 Hz), 1.28 s (3H, CH3), 1.48 m (1H, 7-H,
J = 3.0 Hz), 1.50 m (3H, 9-H2, 8-H), 1.68 m (1H,
1-H), 1.78 s (3H, CH3), 1.98 d.q.q (1H, CHMe2, J =
3.0, 6.9 Hz), 2.05 m (1H, 6-H), 2.30 m (1H, 2-H,
J = 10.0 Hz), 2.46 d.d.d (1H, 2-H, J = 1.0, 6.3,
10.0 Hz), 3.96 d.d (1H, 3-H, J = 6.3, 8.4 Hz), 4.51 d
(1H, OCH2Ph, J = 11.5 Hz), 4.70 d.d (1H, OCH2Ph,
J = 11.5, 10.4 Hz), 5.67 d (1H, 5-H, J = 5.4 Hz),
7.38 m (5H, Harom). 13C NMR spectrum, C, ppm:
15.24 (CH3), 19.76 (CH3), 21.32 (C8), 21.46 (CH3),
The high stereospecificity of the process suggests
a concerted character of transformations in the cyclic
structures at the stages of formation and rearrange-
ment of the ozonide [2]. However, the hydrolysis of
acetal IV (CH2Cl2, i-PrOH, H2O HCl) obtained by
ozonolysis of the same 3-benzyloxy derivative II in
methanol also resulted in formation of ketotriol III.
Thus we can conclude that ozonolytic hydroxylation
____________
24.80 (C2), 26.32 (CH3), 27.68 (CHMe2), 35.06 (C9),
36.88 (C6), 43.68 (C7), 44.10 (C1), 70.42 (OCH2Ph),
71.83 (C10), 78.22 (C3), 128.80 (C5), 135.48 (C4),
127.35, 127.66, 128.33, 138.69 (Carom). Found, %:
C 80.79; H 9.60. C22H32O2. Calculated, %: C 80.44;
H 9.82.
*
This study was financially supported by the Russian Founda-
tion for Basic Research (project no. 01-03-32050).
1070-4280/01/3711-1666$25.00 2001 MAIK Nauka/Interperiodica