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Ligand Coordination- and Dissociation-induced Divergent Allylic Alkylations Using Alkynes by Yuan Huang; Chao Ma; Song Liu; Li-Cheng Yang; Yu Lan; Yu Zhao is a Chemistry article available to read on EtoBox.

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In transition metal catalysis, the nature of ligand coordination plays a vital role in defining the reactivity of the catalytic system. Achieving multi-substrate coordination and coupling by leveraging dynamic ligand dissociation is rare. Here, we report the discovery of such a phenomenon in nickel/copper-co-catalyzed divergent allylic alkylation of vinyl epoxides and aziridines using alkynes. Under otherwise identical conditions, the use of either strong bisphosphine ligands or hemilabile P,N-ligands leads to bimolecular allylic alkynylation or trimolecular dienyne formation, respectively. DFT calculations provide key insights for these ligand-induced divergent reactivities, particularly ligand-dissociation-enabled coordination of three substrates on nickel for trimolecular coupling. This catalytic system couples a remarkably broad range of readily available terminal alkynes with vinyl epoxides, carbonates, and aziridines in high regio- and stereo-selectivity. The utility of the versatile enyne and dienyne products, coupled with the use of abundant nickel/copper catalysts, makes this a practical method in synthetic and medicinal chemistry.

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Author

Yuan Huang; Chao Ma; Song Liu; Li-Cheng Yang; Yu Lan; Yu Zhao

Publisher

Elsevier BV

Published

2021

Language

EN

Field

Chemistry (Physical Sciences)