Divergent Total Syntheses of (-)-Pseudocopsinine and (-)-Minovincinine.

ABSTRACT: Herein, the first total syntheses of (-)-pseudocopsinine (1) and (-)-minovincine (3) from a common intermediate 8 are detailed, enlisting late-stage, hydrogen atom transfer (HAT)-mediated free radical bond formations (C20-C2 and C20-OH, respectively) that are unique to their core or structure. The approach to 1 features an Fe-mediated HAT reaction of the intermediate olefin 2, effecting a transannular C20-C2 free radical cyclization of a challenging substrate with formation of a strained [2.2.1] ring system and reaction of a poor acceptor tetrasubstituted alkene with a hindered secondary free radical to form a bond and quaternary center adjacent to another quaternary center. Central to the assemblage of their underlying Aspidosperma skeleton is a p

SUBMITTER: Zeng X 

PROVIDER: S-EPMC7718306 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature