Loading…

A Kinetic Dearomatization Strategy for an Expedient Biomimetic Route to the Bielschowskysin Skeleton

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 synth...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie 2018-01, Vol.130 (5), p.1330-1335
Main Authors: Scesa, Paul, Wangpaichitr, Medhi, Savaraj, Niramol, West, Lyndon, Roche, Stéphane P.
Format: Article
Language:English
Subjects:
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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. Ein biomimetischer Ansatz für den Aufbau des Kohlenstoffgerüsts von Bielschowskysin, einem Tricyclo[9.3.0.0]tetradecan, verwendet das phylogenetisch verwandte Furanocembranoid Acerosolid als Ausgangsmaterial. Die Synthese beinhaltet eine regio‐ und stereoselektive Furan‐Dearomatisierung, die durch eine kinetisch kontrollierte Halogenabstraktion ermöglicht wird.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201711780