Activation and Functionalization of C–C σ-Bonds of Alkylidene Cyclopropanes at Main Group Centers,Journal of the American Chemical Society

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Activation and Functionalization of C–C σ-Bonds of Alkylidene Cyclopropanes at Main Group Centers
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-06-26 , DOI: 10.1021/jacs.0c03383
Richard Y Kong ₁ , Mark R Crimmin ₁

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Aluminum(I) and magnesium(I) compounds are reported for the C-C σ-bond activation of strained alkylidene cyclopropanes. These reactions result in the formal addition of the C-C σ-bond to main group center either at a single site (Al) or across a metal-metal bond (Mg-Mg). Mechanistic studies suggest that rather than occurring by a concerted oxidative addition, these reactions involve stepwise processes in which substrate binding to the main group metal acts as a precursor to α- or β-alkyl migration steps that break the C-C σ-bond. This mechanistic understanding is used to develop the magnesium-catalyzed hydrosilylation of the C-C σ-bonds of alkylidene cyclopropanes.

中文翻译：

亚烷基环丙烷的 C-C σ-键在主族中心的活化和功能化

据报道，铝（I）和镁（I）化合物可用于应变亚烷基环丙烷的 CC σ 键活化。这些反应导致在单个位点 (Al) 或跨金属-金属键 (Mg-Mg) 将 CC σ-键正式添加到主族中心。机理研究表明，这些反应不是通过协同氧化加成发生，而是涉及逐步过程，其中底物与主族金属结合作为破坏 CC σ 键的 α- 或 β- 烷基迁移步骤的前体。这种机理理解用于开发亚烷基环丙烷的 CC σ 键的镁催化氢化硅烷化。

更新日期：2020-06-26

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