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A general synthesis of chiral 4-amino-4,5-dihydro-3H-dinaphthophosphepines 5a-f is described. The resulting monodentate chiral aminophosphinites have been tested in the rhodium-catalyzed asymmetric hydrogenation of methyl α-acetamidocinnamate and methyl α-acetamidoacrylate. Enantioselectivities up to 96% ee were obtained in the presence of 5a and sodium dodecylsulfonate in toluene.
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