Premium
A Kinetic Dearomatization Strategy for an Expedient Biomimetic Route to the Bielschowskysin Skeleton
Author(s) -
Scesa Paul,
Wangpaichitr Medhi,
Savaraj Niramol,
West Lyndon,
Roche Stéphane P.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201711780
Subject(s) - furan , chemistry , stereoselectivity , natural product , enol , diterpene , combinatorial chemistry , stereochemistry , organic chemistry , catalysis
Bielschowskysin ( 1 ), the flagship of the furanocembranoid diterpene family, has attracted attention from chemists owing to its intriguing and daunting polycyclic architecture and medicinal potential against lung cancer. The high level of functionalization of 1 poses a considerable challenge to synthesis. Herein, a stereoselective furan dearomatization strategy of furanocembranoids was achieved via the intermediacy of chlorohydrins. The stereochemical course of the kinetic dearomatization was established, and the C3 configuration of the resulting exo ‐enol ether intermediates proved to be essential to complete the late‐stage transannular [2+2] photocycloaddition. Overall, this biomimetic strategy starting from the natural product acerosolide ( 9 ) featured an unprecedented regio‐ and highly stereoselective furan dearomatization, which provided rapid access to the pivotal exo ‐enol ethers en route to the intricate bielschowskyane skeleton.