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1,2-Addition of Diethylzinc to a Bis(Imidazolyl)ketone Ligand.

ABSTRACT: In this study, the selective 1,2-addition of diethylzinc to the ketone functionality of BM^diPhIK [bis(1-methyl-4,5-diphenylimidazolyl)ketone] is shown. The reaction product is isolated in a dimeric form with a planar Zn₂(µ-O)₂-motif keeping the two monomers together. This compound can serve as a model for reactive intermediates in the catalytic alkylation of ketones with diorganozinc reagents. Hydrolysis of this binuclear zinc compound leads to isolation of the C-alkylated product in 89?% yield. A reaction pathway is proposed in which BM^diPhIK initially coordinates to diethylzinc as a bidentate bis(nitrogen) ligand. This is followed by the homolytic cleavage of the Zn-Et bond and in-cage recombination of the Et-radical and the Zn-coordinated ligand-centered radical, which is mainly localized on the carbonyl moiety of the ligand.

SUBMITTER: Folkertsma E

PROVIDER: S-EPMC5993287 | biostudies-literature | 2018 Mar

REPOSITORIES: biostudies-literature

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1,2-Addition of Diethylzinc to a Bis(Imidazolyl)ketone Ligand.

Folkertsma Emma E Benthem Sanne H SH Jastrzebski Johann T B H JTBH Lutz Martin M Moret Marc-Etienne ME Klein Gebbink Robertus J M RJM

European journal of inorganic chemistry 20180212 10

In this study, the selective 1,2-addition of diethylzinc to the ketone functionality of BMdiPhIK [bis(1-methyl-4,5-diphenylimidazolyl)ketone] is shown. The reaction product is isolated in a dimeric form with a planar Zn2(µ-O)2-motif keeping the two monomers together. This compound can serve as a model for reactive intermediates in the catalytic alkylation of ketones with diorganozinc reagents. Hydrolysis of this binuclear zinc compound leads to isolation of the C ...[more]

PMID: 29937689

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