Issue 67, 2012

Understanding (the lack of) homolytic substitution chemistry of sulfones

Abstract

High level calculations suggest that homolytic substitution (SH2) by alkyl radicals at sulfur proceeds through a mechanism that is assisted and dominated by LP → SOMO interactions; in the absence of these interactions, SH2 chemistry at sulfur is predicted to be virtually impossible. G3(MP2)-RAD calculations suggest that cyclization of the tert-butylsulfonylbutyl radical 2 (n = 2) proceeds with a rate constant of 1.7 × 10−24 s−1 at 80°, some 28 orders of magnitude slower than its sulfide cousin (n = 0).

Graphical abstract: Understanding (the lack of) homolytic substitution chemistry of sulfones

Supplementary files

Article information

Article type
Communication
Submitted
29 May 2012
Accepted
14 Jun 2012
First published
14 Jun 2012

Chem. Commun., 2012,48, 8326-8328

Understanding (the lack of) homolytic substitution chemistry of sulfones

H. M. Aitken, A. N. Hancock and C. H. Schiesser, Chem. Commun., 2012, 48, 8326 DOI: 10.1039/C2CC33856D

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