From hydrogen autotransfer process to deuterium autotransfer process: The N-trideuteromethylation of amines with deuterated methanol to trideuteromethylated amines catalyzed by a Cp*Ir complex bearing a flexible bridging and functional ligand

A Cp*Ir complex bearing a flexible and functional 6,6'-(OH)(2)-2,2'-dipyridylamine ligand was designed, synthesized and found to be a general and efficient catalyst for the synthesis of trideuteromethylated amines via the N-trideuteromethylation of amines with deuterated methanol based on the proposed deuterium autotransfer process. The synthetic strategy is attractive due to easily available deuterium source, high atom efficiency and environmental friendliness. It was confirmed that OH units in the ligand are crucial for the catalytic activity. Furthermore, a metal-ligand cooperative mechanism was also proposed based on experimental results and DFT calculations. (C) 2022 Elsevier Inc. All rights reserved.

Automated summary

A flexible and functional Cp*Ir complex bearing a 6,6'-(OH)(2)-2,2'-dipyridylamine ligand has been designed, synthesized, and found to be a general and efficient catalyst for the synthesis of trideuteromethylated amines through the N-trideuteromethylation of amines with deuterated methanol. The strategy offers advantages of readily available deuterium source, high atom efficiency, and environmental friendliness. The catalytic activity was confirmed to be dependent on the -OH units in the ligand, and a metal-ligand cooperative mechanism was proposed based on experimental results and DFT calculations.