Formaldehyde dimethylhydrazone: A new neutral reagent for nucleophilic hydroformylation and hydrocyanation

Abstract

The readily available title compound smoothly adds to nitroolefins without any need of base or catalysis, giving β-nitrodimethylhydrazones 3 in high yields. Michael adducts 3 have been successfully transformed into β-nitroaldehydes by ozonolysis and in β-nitronitriles in excellent yields by treatment with MMPP. Therefore, formaldehyde dimethylhydrazone behaves as a new neutral formyl anion and cyanide equivalent, introducing a functionalized carbon unit β to the nitro group of a nitroolefin. Good yields and high stereoselectivities were obtained in the addition of 1 to a nitroolefin group within sugar derivatives, and no epimerization was observed in the cleavage of the dimethylhydrazone group.