Asymmetric Construction of Quaternary Stereocenters by Direct Organocatalytic Amination of α-Substituted α-Cyanoacetates and β-Dicarbonyl Compounds

Abstract
The first organocatalytic highly enantioselective reactions of substituted α-cyanoacetates and β-dicarbonyl compounds with azodicarboxylates are reported. In the presence of 0.1−5 mol % of a quinidine-derived alkaloid β-ICD, optically active quaternary hydrazine adducts are obtained in very high yields and with enantioselectivities up to >98% ee. A two-step procedure for the cleavage of the hydrazine NN bond using SmI2 is also demonstrated.

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