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Metal‐Free σ‐Bond Metathesis in 1,3,2‐Diazaphospholene‐Catalyzed Hydroboration of Carbonyl Compounds
Author(s) -
Chong Che Chang,
Hirao Hajime,
Kinjo Rei
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201408760
Subject(s) - hydroboration , metathesis , catalysis , chemistry , organic chemistry , polymerization , polymer
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 PO bond of the alkoxyphosphine intermediate and the BH bond of pinacolborane as well as the formation of PH and BO 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.