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À propos de : On the Mechanism of the Copper-Catalyzed Enantioselective1,4-Addition of Grignard Reagents to α,β-UnsaturatedCarbonyl Compounds        

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  • On the Mechanism of the Copper-Catalyzed Enantioselective1,4-Addition of Grignard Reagents to α,β-UnsaturatedCarbonyl Compounds
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  • The mechanism of the enantioselective 1,4-addition of Grignard reagents to α,β-unsaturatedcarbonyl compounds promoted by copper complexes of chiral ferrocenyl diphosphines is explored throughkinetic, spectroscopic, and electrochemical analysis. On the basis of these studies, a structure of the activecatalyst is proposed. The roles of the solvent, copper halide, and the Grignard reagent have been examined.Kinetic studies support a reductive elimination as the rate-limiting step in which the chiral catalyst, thesubstrate, and the Grignard reagent are involved. The thermodynamic activation parameters weredetermined from the temperature dependence of the reaction rate. The putative active species and thecatalytic cycle of the reaction are discussed.
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