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

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.

Automated summary

A new method has been developed for the efficient assembly of diversely functionalized polyquinane frameworks, leading to asymmetric total syntheses of various tetraquinane natural products in a concise and divergent manner.