<br/>A recent mechanistic study of a rhenium-catalyzed ortho-directed alkenylation between phenols and terminal alkynes supports a mechanism by which C-C addition proceeds via an oxygen-assisted chelation. This reaction results in exclusively mono-alkenylated products with excellent regioselectivity, though the high temperatures required to drive conversion limit the method’s efficiency and scalability. While the nature of the reaction’s rate limiting step is generally agreed upon, the mechanism of C-C addition is contested.<br/>We investigate the energetic profile of this oxygen-assisted chelation mechanism using density functional methods, and compare the energetics of this pathway to those of other proposed mechanisms of C-C bond formation. A better understanding of this reaction will also shed light on the mechanisms of other regioselective transition-metal catalyzed aromatic substitution reactions.

Computational investigation of a proposed oxygen-assisted chelation as the mechanism of C-C bond formation between phenols and terminal alkynes/alkenes

ACS Fall 2021

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