Asymmetric ruthenium-catalyzed 1,4-additions of aryl thiols to enones
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Updated: Jun 17, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Andrei Bădoiu1, Gerald Bernardinelli, Céline Besnard
1Department of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, CH-1211, Geneva 4, Switzerland.
Abstract:
Well defined, stable, one-point binding ruthenium complexes and selectively bind and activate alpha,beta-unsaturated carbonyl compounds for cycloaddition reactions. These mild Lewis acids catalyze asymmetric 1,4-addition reactions of aryl thiols to enones with product selectivities up to 87% ee. (31)P NMR experiments provide an insight into the intricate equilibria governing the reaction mechanism. The absolute configuration of the major products indicates enones to react in the syn-s-trans orientation. Models based on X-ray structures of the Ru complexes can be used to rationalize selectivity.
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