Divergent Total Syntheses of (−)-Crinipellins Facilitated by a HAT-Initiated Dowd–Beckwith Rearrangement
Yifan Zhao, Jialei Hu, Ruyi Chen, Fengping Xiong, Hujun Xie, Hanfeng Ding
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.
Topics & Concepts
ChemistryEnantioselective synthesisIridiumStereochemistryCombinatorial chemistryCatalysisOrganic chemistrySynthetic Organic Chemistry MethodsAsymmetric Synthesis and CatalysisChemical synthesis and alkaloids