PerspectiveOrganic Chemistry

Rethinking the SN2 reaction

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Science  01 Apr 2016:
Vol. 352, Issue 6281, pp. 32-33
DOI: 10.1126/science.aaf5172

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Summary

The SN2 nucleophilic substitution reaction, X + RY → XR + Y, is a paradigm reaction in organic chemistry (1). The modern understanding of the SN2 reaction mechanism is based on work of Hughes and Ingold (2), who proposed that the nucleophile (X) approaches the carbon atom that bears the leaving group (Y). As a result, the bond between the carbon atom and the leaving group becomes weakened. As this bond breaks and a new bond forms between the nucleophile and the carbon atom, the configuration of the carbon atom is inverted. Analyses of gas-phase reaction rates led to the suggestion of a potential energy surface (PES) with two wells connected by a central barrier transition state (3). Electronic structure calculations have confirmed this picture for some SN2 reactions (4), but recent studies have shown that the actual reaction dynamics may be considerably more complex (see the figure) (58).