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Divergent ring-opening coupling between cyclopropanols and alkynes under cobalt catalysis.

ABSTRACT: Cobalt-diphosphine catalysts promote ring-opening coupling reactions between cyclopropanols and unactivated internal alkynes, affording either ?-alkenyl ketones or multisubstituted cyclopentenol derivatives in good yields with good to excellent regioselectivities. The chemoselectivity between these ?-alkenylation and [3 + 2] annulation reactions, which likely share a cobalt homoenolate as a key catalytic intermediate, is exquisitely controlled by the reaction conditions, with the solvent being a major controlling factor. The reactions are proposed to involve ring opening of cobalt cyclopropoxide into homoenolate, migratory insertion of the alkyne into the Co-C bond, and protodemetalation or intramolecular carbonyl addition of the resulting alkenylcobalt species. The feasibility of these reaction steps was supported by DFT calculations.

SUBMITTER: Yang J

PROVIDER: S-EPMC6124909 | biostudies-other | 2018 Sep

REPOSITORIES: biostudies-other

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Divergent ring-opening coupling between cyclopropanols and alkynes under cobalt catalysis.

Yang Junfeng J Shen Yixiao Y Lim Yang Jie YJ Yoshikai Naohiko N

Chemical science 20180716 34

Cobalt-diphosphine catalysts promote ring-opening coupling reactions between cyclopropanols and unactivated internal alkynes, affording either β-alkenyl ketones or multisubstituted cyclopentenol derivatives in good yields with good to excellent regioselectivities. The chemoselectivity between these β-alkenylation and [3 + 2] annulation reactions, which likely share a cobalt homoenolate as a key catalytic intermediate, is exquisitely controlled by the reaction conditions, with the solvent being a ...[more]

PMID: 30210767

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