Rates and Equilibria of the Michael-Type Addition of Benzenethiol to 2-Cyclopenten-1-ones

The triethylamine-catalyzed addition reactions of benzenethiol to 2-cyclopenten-1-one and its 2- and 3-methyl derivatives have been found to be appreciably reversible in chloroform solution. Rates and equilibria have been carefully measured at 25 °C in order to assess the negative influence on addit...

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Bibliographic Details
Published in:Journal of organic chemistry 1999-10, Vol.64 (22), p.8122-8126
Main Authors: van Axel Castelli, Valeria, Bernardi, Fernando, Dalla Cort, Antonella, Mandolini, Luigi, Rossi, Ivan, Schiaffino, Luca
Format: Article
Language:English
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Summary:The triethylamine-catalyzed addition reactions of benzenethiol to 2-cyclopenten-1-one and its 2- and 3-methyl derivatives have been found to be appreciably reversible in chloroform solution. Rates and equilibria have been carefully measured at 25 °C in order to assess the negative influence on addition exerted by methyl groups substituted on the carbon−carbon double bond. 2-Methyl-2-cyclopenten-1-one has been found to react with benzenethiol under kinetic control to give the cis adduct as the sole detectable product in a highly stereoselective anti addition process. However, on prolonged reaction times the system slowly evolved toward a new state of equilibrium in which the more stable trans adduct, derived from a syn addition mode, was the predominant isomer.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo9906882