Hydrophosphination of CO2 and subsequent formate transfer in the 1,3,2-diazaphospholene-catalyzed N-formylation of amines.
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.
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore 637371 (Singapore).
Che Chang
CC
Chong
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore 637371 (Singapore). rkinjo@ntu.edu.sg.
Rei
R
Kinjo
CO2 activation; N-formylation; hydrophosphination; hydrosilylation; metal-free catalysis