B. B. Shingate et al. / Tetrahedron Letters 52 (2011) 6007–6010
6009
O
O
O
RuCl3, tBuOOH
Cyclohexane, 20 °C,
6 h, 89%
AcO
AcO
O
5
4
OH
OH
O
O
RuCl3, tBuOOH
Cyclohexane, 20 °C,
6 h, 93%
AcO
AcO
AcO
AcO
O
O
7
9
6
8
O
O
RuCl3, tBuOOH
Cyclohexane, 20 °C,
6 h, 78%
OAc
OAc
OH
OH
O
RuCl3 ,tBuOOH
Cyclohexane, 20 °C,
6 h, 87%
AcO
AcO
O
11
10
Scheme 2. Allylic oxidation of lanosteryl acetate derivatives.
2. (a) Parish, E. J.; Nanduri, V. B. B.; Kohl, H. H.; Taylor, F. R. Lipids 1986, 21, 27–30;
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hydroperoxide resulted into the formation of 7,11-oxo derivative
11 in 87% yield (Scheme 2). Formation of compounds 8, 9, and 11
has been confirmed by IR, 1H NMR, 13C NMR, and mass spectro-
scopic analysis.16
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In conclusion, we have achieved the allylic oxidation of D8(9)
-
lanosterol derivatives using t-butyl hydroperoxide in the presence
of ruthenium chloride (RuCl3) in cyclohexane to the corresponding
7,11-dienones for the first time in good yields. Work on the study
of structure–activity relationship by modifying carbonyl groups for
getting more potent lead molecules is in progress. The advantages
of the present procedure are relatively short reaction times and
high yield.
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Acknowledgments
B.B.S. thanks the University Grants Commission, New Delhi for
Research Fellowship. The Emeritus Scientist Scheme awarded to
B.G.H. by the Council of Scientific and Industrial Research, New
Delhi, is gratefully acknowledged.
Supplementary data
Supplementary data associated (general procedures and spec-
tral data) with this Letter can be found, in the online version, at
References and notes
1. Kanduutsch, A. A.; Chen, H. W.; Heiniger, H.-J. Science 1978, 201, 498–501.