Chiral inducers with (1R,2R)-1,2-diaminocyclohexane core for organo- and metallocatalysis

A P*-chiral diamidophosphite ligand of the 1,3,2-diazaphospholidine series was obtained by direct phosphorylation of N-[(1R,2R)-2-(tert-butoxycarbonylaminocyclohexyl)]-N′-[(1R)-1-(hydroxymethyl)propyl]oxalamide. The use of this ligand made it possible to reach 98% ee in the Pd-catalyzed allylation involving (E)-1,3-diphenylallyl acetate, 81% ee in the allylation of ethyl 2-oxocyclohexane-1-carboxylate with cinnamyl acetate, 78% ee in the Rh-catalyzed hydrogenation of methyl (Z)-2-acetamido-3-phenylacrylate, and 32% ee in the Rh- and Ir-catalyzed hydrosilylation of (E)-N-(4-methoxyphenyl)-1-phenylethan-1-imine with diphenylsilane. The above mentioned oxalamide provides up to 50% ee in the organocatalytic reduction of the same imine.