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Asymmetric Rh-catalyzed hydrogenation using a furanoside phosphite-phosphoroamidite and diphosphoroamidite ligand
Mercedes Coll1, Oscar Pàmies, Montserrat Diéguez
1Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Tarragona, Spain.
Abstract:
A furanoside phosphite-phosphoroamidite and diphosphoroamidite ligand library L1-L5a-f was tested in the asymmetric Rh-catalyzed hydrogenation of α,β-unsaturated carboxylic acid derivatives and enamides. Enantioselectivity depended strongly on the ligand parameters. High enantioselectivities were obtained in the reduction of dimethyl itaconate (up to >99% ee), α-dehydroamino acid esters (up to 99% ee) and several enamides (up to 92% ee). Kinetic and NMR studies on the intermediates of the catalytic cycle of the reaction indicate that the [Rh(P(1)-P(2))(substrate)](+) species is the resting state of the reaction and that the rate dependence is first order in rhodium and hydrogen pressure and zeroth order in the substrate.
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