Nucleophilic Vinylic Substitution. A Theoretical Study

Drora Cohen, Rony Bar, Sason S. Shaik

Research output: Contribution to journalArticlepeer-review

53 Scopus citations

Abstract

Reactivity trends in nucleophilic vinylic substitutions are discussed in a two-pronged approach. Ab initio computations of eight reactions are performed. The results of transition-state geometries, reaction barriers, and mechanistic variety are used in conjunction with experimental evidence as the data stock to be patterned. The state correlation diagram is utilized for this last purpose. Potential energy profiles are constructed and the origin of barriers is projected. Expected patterns are predicted and compared with the computed and experimental data in the following areas: (a) the spectrum of mechanism, stepwise, and single-step reactions; (b) trends in reaction barriers and “intrinsic barriers” for attack and leaving-group expulsion steps; (c) trends in transition-state geometries and the role of geometric distortions.

Original languageEnglish
Pages (from-to)231-240
Number of pages10
JournalJournal of the American Chemical Society
Volume108
Issue number2
DOIs
StatePublished - 1986
Externally publishedYes

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