Abstract

A family of chiral (3,3′-di-tert-butyl-5,5′,6,6′-tetramethyl-2,2′-biphenol-derived) phosphine−phosphite ligands (P−OP) with a substituted ethane backbone has been synthesized and the performance of these ligands in the Rh-catalyzed enantioselective hydrogenation and hydroformylation of several representative olefins analyzed. Corresponding cationic rhodium complexes provide highly enantioselective catalysts for the hydrogenation of methyl (Z)-α-acetamidocinnamate (MAC) and dimethyl itaconate. The catalyst comparison indicates that, for the two substrates, product configuration is determined by the configuration of the phosphite. Regarding matching and mismatching effects in these hydrogenations, small effects were observed in the reduction of MAC, while for the itaconate the bigger difference between the matched and mismatched cases was of 21% ee. On the other hand, Rh catalysts based on P−OP ligands showed good levels of activity and regioselectivity in the hydroformylation of styrene and allyl cyanide, ...

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