A General Strategy for the Construction of Calyciphylline A‐Type Alkaloids: Divergent Total Syntheses of (−)‐Daphenylline and (−)‐Himalensine A

Angewandte Chemie International Edition
2021.0

Abstract

An efficient general strategy for the synthesis of the Daphniphyllum alkaloids via the rapid construction of a common core intermediate has been established, based on which a divergent total synthesis of (-)-daphenylline and (-)-himalensine A has been accomplished in 16 and 19 steps, respectively. The present work features an enantioselective Mg(ClO4)(2)-catalyzed intramolecular amidocyclization to construct the aza-bridged core structure; a Cu-catalyzed intramolecular cyclopropanation and subsequent phosphine-catalyzed Cope-type rearrangement to furnish the himalensine A scaffold; and a one-pot Diels-Alder/aromatization method to assemble the aromatic skeleton of daphenylline.

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