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Divergent Total Syntheses of (-)-Crinipellins Facilitated by a HAT-Initiated Dowd-Beckwith Rearrangement

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Journal J Am Chem Soc
Specialty Chemistry
Date 2022 Feb 3
PMID 35112847
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Abstract

A hydrogen atom transfer (HAT)-initiated Dowd-Beckwith rearrangement reaction was developed, which enables the efficient assembly of diversely functionalized polyquinane frameworks. By incorporation of an iridium-catalyzed regio- and enantioselective hydrogenation and a diastereocontrolled ODI-[5+2] cycloaddition/pinacol rearrangement cascade reaction, the asymmetric total syntheses of eight tetraquinane natural products, including (-)-crinipellins A-F and (-)-dihydrocrinipellins A and B, have been achieved in a concise and divergent manner.

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