Hydrophosphination of CO2 and Subsequent Formate Transfer in the 1,3,2-Diazaphospholene-Catalyzed N-Formylation of Amines.

Angewandte Chemie (International ed. in English)

PubMedID: 26276547

Chong CC, Kinjo R. Hydrophosphination of CO2 and Subsequent Formate Transfer in the 1,3,2-Diazaphospholene-Catalyzed N-Formylation of Amines. Angew Chem Int Ed Engl. 2015;.
Hydrophosphination of CO2 with 1,3,2-Diazaphospholene (NHP-H; 1) afforded phosphorus formate (NHP-OCOH; 2) through the formation of a bond between the electrophilic phosphorus atom in 1 and the oxygen atom from CO2 , along with hydride transfer to the carbon atom of CO2. Transfer of the formate from 2 to Ph2 SiH2 produced Ph2 Si(OCHO)2 (3) in a reaction that could be carried out in a catalytic manner by using 5 mol?% of 1. These elementary reactions were applied to the metal-free catalytic N-formylation of amine derivatives with CO2 in one pot under ambient conditions.