Synthesis of Hydrazines by Rh(II)-Catalyzed N–H Amination of Aliphatic Amines and α-Amino Acids

Dirhodium(II)-Catalyzed Synthesis of N-(Arylsulfonyl)hydrazines by N–H Amination of Aliphatic Amines: M. Ito, Y. Hasegawa, S. Saito, A. Onda, K. Higuchi, S. Sugiyama
Synlett 2022, 33, DOI: 10.1055/s-0041-1737759

Nitrogen–nitrogen bonds are frequently encountered in natural and bioactive compounds. In particular, the hydrazine moiety represents a privileged structural motif which is present in important molecules, such as α-hydrazino acids. However, the number of methods for intermolecularly constructing N–N bonds is still quite limited, especially those based on metal catalysis using nucleophilic primary or secondary amines as substrates. This is mainly due to their propensity to poison the catalyst by strongly coordinating to the metal center. Recently, the group of Dr. Motoki Ito and Professor Shigeo Sugiyama from Meiji Pharmaceutical University (Tokyo, Japan) reported a new efficient approach to this synthetic problem, allowing for an effective preparation of aliphatic hydrazines and α-hydrazino acids via dirhodium(II)-catalyzed N–N bond formation.

Dr. Ito said: “We developed an N–H amination reaction of aliphatic amines with Rh(II)-nitrene species for the first time and demonstrated that the reaction enabled the synthesis of pharmaceutically interesting α-hydrazino acids from α-amino acids.”