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

Abstract

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.