Synthesis 2018; 50(22): 4395-4412
DOI: 10.1055/s-0037-1611053
© Georg Thieme Verlag Stuttgart · New York

Directed ortho Metalation (DoM)-Linked Corriu–Kumada, Negishi, and Suzuki–Miyaura Cross-Coupling Protocols: A Comparative Study

Claude A. Quesnelle
Victor Snieckus*
We are grateful to NSERC Canada, Discovery Grant (DG 05698) for support of our synthetic programs and CQ thanks NSERC for a graduate fellowship.
Further Information

Publication History

Received: 09 July 2018

Accepted after revision: 21 August 2018

Publication Date:
05 October 2018 (online)

Dedicated to Scott Denmark: By this, we (and KB in absentia) are celebrating your creativity and stellar achievements.

Published as part of the Special Section dedicated to Scott E. Denmark on the occasion of his 65th birthday.


A systematic study of the widely used, titled name reaction transition-metal-catalyzed cross-coupling reactions with attention to context with the directed ortho metalation (DoM) is reported. In general, the Suzuki–Miyaura and Negishi protocols show greater scope and better yields than the Corriu–Kumada variant, although the latter qualitatively proceeds at fastest rate but has low functional group tolerance. The Negishi process is shown to be useful for substrates with nucleophile and base-sensitive functionality and it is comparable to the Suzuki–Miyaura reaction in efficiency. The link of these cross-coupling reactions to the DoM strategy lends itself to the regioselective construction of diversely substituted aromatics and heteroaromatics.

Supporting Information

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