Radical Stabilization Algorithm as a Predictive Tool for Novel and Reported Noncanonical Thiele’s Acid AnaloguesThis work was supported by the National Science and Engineering Research Council of Canada (NSERC), and by the Michael Smith Foundation for Health Research.
Received: 25 July 2017
Accepted after revision: 08 September 2017
06 October 2017 (eFirst)
This paper is dedicated to Professor Victor Snieckus, in honour of his 80th birthday
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.