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Synthesis of Hydrazines (Hydrazides)


Recent Literature

The electrophilic amination of primary aliphatic and aromatic amines with a diethylketomalonate-derived oxaziridine affords the corresponding N-Boc hydrazines in good to excellent yields. The method allows a one-pot synthesis of pyrazoles from primary amines.
A. Armstrong, L. H. Jones, J. D. Knight, R. D. Kelsey, Org. Lett., 2005, 7, 713-716.

A small ring phosphacycle (phosphetane) catalyzes the synthesis of unsymmetrical hydrazines by cross-selective intermolecular NN reductive coupling of nitroarenes and anilines in the presence of a hydrosilane as the terminal reductant. The reaction offers good chemoselectivity and functional group tolerance.
G. Li, S. P. Miller, A. T. Radosevich, J. Am. Chem. Soc., 2021, 143, 14464-14469.

A nickel-catalyzed N-N cross-coupling of O-benzoylated hydroxamates with a broad range of aryl and aliphatic amines provides hydrazides in an up to 81% yield. Experimental evidence implicates the intermediacy of electrophilic Ni-stabilized acyl nitrenoids and the formation of a Ni(I) catalyst via silane-mediated reduction.
J. P. Barbor, V. N. Nair, K. R. Sharp, T. D. Lohrey, S. E. Dibrell, T. K. Shah, M. J. Walsh, S. E. Reisman, B. M. Stoltz, J. Am. Chem. Soc., 2023, 145, 15071-15077.

A broadly applicable procedure for an aza-Lossen rearrangement converts amines into complex hydrazine derivatives in two steps under safe, mild conditions. This method allows the chemoselective formation of N-N bonds, resulting in the synthesis of cyclic and acyclic products while avoiding side reactions of the amphoteric (ambident) nitrogen-substituted isocyanate intermediate.
D. E. Polat, D. D. Brzezinski, A. M. Beauchemin, Org. Lett., 2019, 21, 4849-4852.