1,2-Addition of Diethylzinc to a Bis(Imidazolyl)ketone Ligand,European Journal of Inorganic Chemistry

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1,2-Addition of Diethylzinc to a Bis(Imidazolyl)ketone Ligand
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2018-02-12 , DOI: 10.1002/ejic.201701363
Emma Folkertsma ₁ , Sanne H Benthem ₁ , Johann T B H Jastrzebski ₁ , Martin Lutz ₂ , Marc-Etienne Moret ₁ , Robertus J M Klein Gebbink ₁

Affiliation

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‐alkylated product in 89 % yield. A reaction pathway is proposed in which BMdiPhIK 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.

中文翻译：

二乙基锌与双(咪唑基)酮配体的 1,2-加成

在本研究中，显示了二乙基锌选择性 1,2 加成到 BMdiPhIK [双(1-甲基-4,5-二苯基咪唑基)酮]的酮官能团上。反应产物以二聚体形式分离，平面 Zn2(μ-O)2-基序将两个单体保持在一起。该化合物可以作为二有机锌试剂催化酮类烷基化反应中间体的模型。这种双核锌化合物的水解导致 C-烷基化产物的分离，产率 89%。提出了一种反应途径，其中 BMdiPhIK 最初与二乙基锌配位作为二齿双（氮）配体。接下来是 Zn-Et 键的均裂以及 Et 自由基和 Zn 配位配体中心自由基的笼内重组，该自由基主要位于配体的羰基部分。

更新日期：2018-02-12

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