Cobalt-Catalyzed Formation of Grignard Reagents via C–O or C–S Bond Activation,The Journal of Organic Chemistry

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Cobalt-Catalyzed Formation of Grignard Reagents via C–O or C–S Bond Activation
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2022-06-22 , DOI: 10.1021/acs.joc.2c00221
Ewa Pietrasiak ₁ , Seongmin Ha ₁ , Seungwon Jeon ₁ , Jongheon Jeong ₁ , Jiyeon Lee ₁ , Jongcheol Seo ₁ , Eunsung Lee ₁

Affiliation

C(aryl)–OMe bond functionalization catalyzed by cobalt(II) chloride in combination with a nacnac-type ligand and magnesium as a reductant is reported. Borylation and benzoylation of aryl methoxides are demonstrated, and C(aryl)–SMe bond borylation can be achieved under similar conditions. This is the first example of achieving these transformations using cobalt catalysis. Mechanistic studies suggest that a Grignard reagent is generated as an intermediate in a rare example of a magnesiation via a C–O bond activation reaction. Indeed, an organomagnesium species could be directly observed by electrospray ionization mass spectroscopic analysis. Kinetic experiments indicate that a heterogeneous cobalt catalyst performs the C–O bond activation.

中文翻译：

通过 C-O 或 C-S 键活化钴催化形成格氏试剂

报道了由氯化钴（II）与 nacnac 型配体和镁作为还原剂催化的 C（芳基）-OMe 键官能化。证明了芳基甲醇盐的硼化和苯甲酰化，并且可以在类似条件下实现 C(芳基)-SMe 键硼化。这是使用钴催化实现这些转化的第一个例子。机理研究表明，格氏试剂是通过C-O 键活化反应产生的一个罕见的镁化例子中的中间体。事实上，有机镁物种可以通过电喷雾电离质谱分析直接观察到。动力学实验表明，非均相钴催化剂进行 C-O 键活化。

更新日期：2022-06-22

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