Rates and Equilibria of the Michael-Type Addition of Benzenethiol to 2-Cyclopenten-1-ones - PubMed (original) (raw)
. 1999 Oct 29;64(22):8122-8126.
doi: 10.1021/jo9906882.
Affiliations
- PMID: 11674725
- DOI: 10.1021/jo9906882
Rates and Equilibria of the Michael-Type Addition of Benzenethiol to 2-Cyclopenten-1-ones
Valeria van Axel Castelli et al. J Org Chem. 1999.
Abstract
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 degrees 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.
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