Metal-free σ-bond metathesis in 1,3,2-diazaphospholene-catalyzed hydroboration of carbonyl compounds

• Main Authors: Chong, Che Chang, Hirao, Hajime, Kinjo, Rei
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2015
• Subjects: DRNTU::Science::Chemistry::Organic chemistry::Carbanions
• Online Access: https://hdl.handle.net/10356/103939; http://hdl.handle.net/10220/24628
• Institution: Nanyang Technological University

The first metal-free catalytic hydroboration of carbonyl derivatives has been developed in which a catalytic amount of 1,3,2-diazaphospholene effectively promotes a hydroboration reaction of aliphatic and aromatic aldehydes and ketones. The reaction mechanism involves the cleavage of both the P-O bond of the alkoxyphosphine intermediate and the B-H bond of pinacolborane as well as the formation of P-H and B-O bonds. Thus, the reaction proceeds through a non-metal σ-bond metathesis. Kinetic and computational studies suggest that the σ-bond metathesis occurred in a stepwise but nearly concerted manner.