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Addition of Methyl Radical to Substituted Alkenes: A Theoretical Study of the Reaction Mechanism
Author(s) -
Wong Ming Wah,
Pross Addy,
Radom Leo
Publication year - 1993
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.199300048
Subject(s) - chemistry , alkene , reactivity (psychology) , nucleophile , computational chemistry , ab initio , methyl radical , reaction mechanism , concerted reaction , polar , medicinal chemistry , photochemistry , radical , organic chemistry , catalysis , medicine , physics , alternative medicine , pathology , astronomy
Abstract Ab initio calculations at the QCISD(T)/6–311G ** level have been carried out to study the addition of the methyl radical to a series of substituted alkenes, and the results analyzed with the aid of the curve‐crossing model. It is found that (a) reaction exothermicity is the main factor that dominates reactivity, (b) polar contributions to the transition states are generally small and of minor energetic consequences, and (c) the general observation that π‐electron‐accepting substituents in the alkene enhance reactivity is a secondary correlation that is a consequence of the effect of these substituents on reaction exothermicity. There is no evidence for the prevalent view that the methyl radical is generally nucleophilic towards alkenes.