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Eliminative Ring Opening of Oxiranium Ions in the Gas Phase
Author(s) -
Renzi Gabriele,
Roselli Graziella,
Grandinetti Felice,
Filippi Antonello,
Speranza Maurizio
Publication year - 2000
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/(sici)1521-3773(20000502)39:9<1673::aid-anie1673>3.0.co;2-3
Subject(s) - nucleophile , chemistry , gas phase , ring (chemistry) , ion , stereochemistry , phase (matter) , computational chemistry , reaction mechanism , mechanism (biology) , catalysis , organic chemistry , physics , quantum mechanics
An unprecedented reaction governed by stereoelectronic factors : Eliminative ring opening of epoxides, unknown in acidic solution owing to the predominance of the competing nucleophilic displacement, can be made accessible in the gas phase. The kinetic evidence, supported by a comprehensive theoretical study on a model system, points to a concerted elimination mechanism in which stereochemistry is controlled by stereoelectronic and conformational factors (in the scheme, the E isomer is formed more readily than the Z isomer; k E > k Z ).