Asymmetric ruthenium-catalyzed 1,4-additions of aryl thiols to enones.
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.
Bădoiu
Andrei
A
Department of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, CH-1211, Geneva 4, Switzerland.
Bernardinelli
Gerald
G
Besnard
Céline
C
Kündig
E Peter
EP
D000475:Alkenes / Q000737:chemistry*; D001665:Binding Sites; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D007659:Ketones / Q000737:chemistry*; D017975:Ruthenium Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D000475:Alkenes; D007659:Ketones; D017975:Ruthenium Compounds; D013438:Sulfhydryl Compounds