Metal‐Free σ‐Bond Metathesis in 1,3,2‐Diazaphospholene‐Catalyzed Hydroboration of Carbonyl Compounds |
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Authors: | Che Chang Chong Prof?Dr Hajime Hirao Prof?Dr Rei Kinjo |
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Institution: | Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Nanyang Link 21, Singapore 637371 (Singapore) |
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Abstract: | 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. |
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Keywords: | hydroboration main‐group catalysts metal‐free catalysis phosphanes σ ‐bond metathesis |
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