Bioinspired Total Synthesis of the Dimeric Indole Alkaloid (+)‐Haplophytine by Direct Coupling and Late‐Stage Oxidative Rearrangement

Abstract

AbstractA bioinspired convergent total synthesis of (+)‐haplophytine, a dimeric indole alkaloid with diazabicyclo[3.3.1]nonane and hexacyclic aspidosperma segments, is described. This synthesis involves the direct coupling of the two segments in a AgNTf2‐mediated Friedel–Crafts reaction and construction of the diazabicyclo[3.3.1]nonane skeleton through late‐stage chemoselective aerobic oxidation of the 1,2‐diaminoethene moiety and a sequential semipinacol‐type rearrangement.