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Published July 6, 2018 | Accepted Version + Supplemental Material
Journal Article Open

Wolff/Cope Approach to the AB Ring of the Sesterterpenoid Variecolin


A stereoselective synthesis of the AB ring of the complex sesterterpenoid variecolin is presented. Our strategy features the development of a tandem Wolff/Cope rearrangement of α-diazo cyclobutyl ketones for the construction of fused, 8-membered carbocycles. Preliminary studies revealed a facile Wolff rearrangement but a difficult vinyl ketene cyclobutane Cope rearrangement. We have leveraged an efficient microwave-promoted tandem rearrangement to prepare the desired functionalized cyclooctadienones that we envision as potential key intermediates in the convergent synthesis of variecolin.

Additional Information

© 2018 American Chemical Society. Received: November 22, 2017; Published: January 4, 2018. Special Issue: Synthesis of Antibiotics and Related Molecules. The authors thank the NIH-NIGMS (R01GM080269), Eli Lilly (predoctoral fellowship to M.R.K.), the Danish Council for Independent Research/Natural Sciences (postdoctoral fellowship to T.J.), Amgen, AbbVie, Bristol-Myers Squibb, Boehringer-Ingelheim, Merck, and Caltech for generous financial support. Dr. Takeharu Toyoshima and Angela Guerrero are acknowledged for contributions to substrate preparation and reaction scouting. Drs. David VanderVelde and Scott Ross of the Caltech NMR facility are thanked for invaluable assistance with NMR experiments and helpful discussions. Lawrence Henling and Michael Day are gratefully acknowledged for X-ray crystallographic structural determination. Dr. Mona Shahgholi and Naseem Torian are acknowledged for assistance with high-resolution mass spectrometry. The authors declare no competing financial interest.

Attached Files

Accepted Version - nihms945199.pdf

Supplemental Material - jo7b02972_si_001.pdf

Supplemental Material - jo7b02972_si_002.cif


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