Hydrophosphination of CO₂ and Subsequent Formate Transfer in the 1,3,2‐Diazaphospholene‐Catalyzed <i>N</i>‐Formylation of Amines

Abstract

Abstract Hydrophosphination of CO 2 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 CO 2 , along with hydride transfer to the carbon atom of CO 2 . Transfer of the formate from 2 to Ph 2 SiH 2 produced Ph 2 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 CO 2 in one pot under ambient conditions.