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Synfacts 2008(9): 0908-0908  
DOI: 10.1055/s-2008-1077992
Synthesis of Natural Products and Potential Drugs
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of (±)-Desoxyhypnophilin

Contributor(s):Philip Kocienski, Arndt W. Schmidt
L. Jiao, C. Yuan, Z.-X. Yu*
Peking University, Beijing, P. R. of China
Tandem Rh(I)-Catalyzed [(5+2)+1] Cycloaddition/Aldol Reaction for the Construction of Linear Triquinane Skeleton: Total Syntheses of (±)-Hirsutene and (±)-Desoxyhypnophilin
J. Am. Chem. Soc.  2008,  130:  4421-4430  
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Publication History

Publication Date:
22 August 2008 (online)

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Key words

[5+2+1] cycloaddition - bicyclics - rhodium - hirsutene - 1-desoxyhypno­-philin

Significance

By utilization of cyclopropyl-substituted dienes as substrates, the scope of Wender’s Rh(I)-catalyzed [5+2+1] cycloaddition of vinyl­cyclopropanes and alkynes has been considerably extended. Thus, the linear triquinane skeleton is constructed in a one-pot procedure.

Comment

The trans-[6.3.0] product arising from (E)-C did not undergo aldol addition (E → G). SeO2 oxidation of H furnished a mixture of the desired diol and the corresponding hydroxyketone. Both were converted into I. The final epoxidation has been described previously (D. C. Harrowven, M. C. Lucas, P. D. Howes Tetrahedron 2001, 57, 9157).

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