Journal of the American Chemical Society, Vol.141, No.32, 12507-12512, 2019
Driving Recursive Dehydration by P-III/P-V Catalysis: Annulation of Amines and Carboxylic Acids by Sequential C-N and C-C Bond Formation
A method for the annulation of amines and carboxylic acids to form pharmaceutically relevant azaheterocycles via organophosphorus P-III/P-V redox catalysis is reported. The method employs a phosphetane catalyst together with a mild bromenium oxidant and terminal hydrosilane reductant to drive successive C-N and C-C bond-forming dehydration events via the serial action of a catalytic bromophosphonium intermediate. These results demonstrate the capacity of P-III/P-V redox catalysis to enable iterative redox-neutral transformations in complement to the common reductive driving force of the P-III/P-V couple.