Synlett
DOI: 10.1055/s-0036-1588583
letter
© Georg Thieme Verlag Stuttgart · New York

Radical Stabilization Algorithm as a Predictive Tool for Novel and Reported Noncanonical Thiele’s Acid Analogues

Jun Chen, Lingxiao Lu, Jeremy E. Wulff*
  • Department of Chemistry, University of Victoria, Victoria, BC, V8W 3V6, Canada   Email: wulff@uvic.ca
This work was supported by the National Science and Engineering ­Research Council of Canada (NSERC), and by the Michael Smith Foundation for Health Research.
Further Information

Publication History

Received: 25 July 2017

Accepted after revision: 08 September 2017

Publication Date:
06 October 2017 (eFirst)

This paper is dedicated to Professor Victor Snieckus, in honour of his 80th birthday

Abstract

We recently showed that a simple radical-stabilization algorithm outperformed traditional frontier-molecular orbital methods for rationalizing the outcome of the venerable Thiele’s acid (or ester) Diels–Alder dimerization. In the present Communication, we describe a novel noncanonical Thiele-type dimerization of a cyclopentadiene phosphine oxide, and show that when steric factors are taken into account the ­radical-stabilization method once again correctly rationalizes the regio­chemical outcome for the reaction. We further show that the method appears to be general for all known Thiele- and half-Thiele dimerization events.

Supporting Information