Synlett
DOI: 10.1055/s-0036-1590801
cluster
© Georg Thieme Verlag Stuttgart · New York

Lewis Acid Assisted C–CN Cleavage of Benzonitrile Using [(dippe)NiH]2

Brett D. Swartz, William W. Brennessel, William D. Jones*
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Publication History

Received: 05 May 2017

Accepted: 23 May 2017

Publication Date:
20 July 2017 (eFirst)

Published as part of the Cluster C–C Activation

Abstract

Reactions of [(dippe)NiH]2 with benzonitrile and varying concentrations of Lewis acids (primarily BPh3 and BF3) have shown a dramatic variation of reaction rate compared to the same reaction without Lewis acids. When less than one equivalent of Lewis acid is used, the reaction rate is as much as 100 times greater than without Lewis acid. Boron exchange was observed with less than one equivalent of Lewis acid allowing the formation of a Ni(0)–η2-aryl complex (observed by low-temperature NMR and calculations) to which the Lewis acid is postulated to re-coordinate as the rate-limiting step allowing the formation of a stable Ni(II) product. When one equivalent or greater of Lewis acid is used, the reaction shows dramatic inhibition even compared to the reaction without Lewis acid. Lewis acid dissociation can be considered as the rate-limiting step under these conditions. The overall work detailed herein has shown the importance of Lewis acids in the activation of benzonitriles due to the strengthening of the C–N bond allowing for increased stabilization of the products.

Supporting Information