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铁催化的C(sp)-C(sp)偶联反应构建季碳中心

Iron-Catalyzed C(sp)-C(sp) Coupling to Construct Quaternary Carbon Centers.

作者信息

Zhang Qiao, Liu Xiang-Yu, Zhang Yan-Dong, Huang Ming-Yao, Zhang Xin-Yu, Zhu Shou-Fei

机构信息

Frontiers Science Center of New Organic Matters, State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China.

Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China.

出版信息

J Am Chem Soc. 2024 Feb 28;146(8):5051-5055. doi: 10.1021/jacs.3c14032. Epub 2024 Feb 19.

Abstract

The construction of quaternary carbon centers via C-C coupling protocols remains challenging. The coupling of tertiary C(sp) with secondary or tertiary C(sp) counterparts has been hindered by pronounced steric clashes and many side reactions. Herein, we have successfully developed a type of bisphosphine ligand iron complex-catalyzed coupling reactions of tertiary alkyl halides with secondary alkyl zinc reagents and efficiently realized the coupling reaction between tertiary C(sp) and secondary C(sp) with high selectivity for the initial instance, which provided an efficient method for the construction of quaternary carbon centers with high steric hindrance. The combination of an iron catalyst and directing group of the substrate makes the great challenging transformation possible.

摘要

通过碳-碳偶联方法构建季碳中心仍然具有挑战性。叔碳C(sp)与仲碳或叔碳C(sp)对应物的偶联受到明显的空间位阻冲突和许多副反应的阻碍。在此,我们成功开发了一种双膦配体铁络合物催化的叔卤代烃与仲烷基锌试剂的偶联反应,并首次高效且选择性地实现了叔碳C(sp)与仲碳C(sp)之间的偶联反应,为构建具有高空间位阻的季碳中心提供了一种有效方法。铁催化剂与底物导向基团的结合使这一极具挑战性的转化成为可能。

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