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Synfacts 2007(8): 0783-0783  
DOI: 10.1055/s-2007-968720
Synthesis of Natural Products and Potential Drugs
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Spirotenuipesine A

Contributor(s):Philip Kocienski, Thomas Snaddon
M. Dai, S. J. Danishefsky*
Columbia University and Sloan-Kettering Institute for Cancer Research, New York, USA
The Total Synthesis of Spirotenuipesines A and B
J. Am. Chem. Soc.  2007,  129:  3498-3499  
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Further Information

Publication History

Publication Date:
24 July 2007 (online)

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Key words

carbenoids - cyclopropanation - Barton-McCombie deoxygenation - Diels-Alder reaction

Significance

Spirotenuipesines A and B are isolated from the Paecilomuyces tenuipes fungus. They show activity against 1321N1 human astrocytoma cells by inducing discharge of neuro­trophic factors. Key to this synthesis is an intermolecular Diels-Alder reaction to prepare a spiroenone (G to I).

Comment

Decomposition of α-diazoester A with B (see E. J. Corey, A. G Myers Tetrahedron Lett. 1984, 25, 3559; R. G. Charles J. Org. Chem. 1957, 22, 677) gave C by intramolecular cyclopropanation. Radical-mediated deoxygenation-cyclopropane fragmentation of D afforded alkene E. Later, intermolecular Diels-Alder reaction of enone G and diene H gave spirocycle I.

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