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过渡金属配合物催化芳烃C(sp)-H氧化加成反应中选择性测定的教程

A Tutorial on Selectivity Determination in C(sp)-H Oxidative Addition of Arenes by Transition Metal Complexes.

作者信息

Pabst Tyler P, Chirik Paul J

机构信息

Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.

出版信息

Organometallics. 2021 Apr 12;40(7):813-831. doi: 10.1021/acs.organomet.1c00030. Epub 2021 Mar 16.

DOI:10.1021/acs.organomet.1c00030
PMID:33867622
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8045024/
Abstract

A Tutorial on factors that determine the selectivity in C(sp)-H activation and functionalization reactions involving two-electron oxidative addition processes with transition metals is presented. The interplay of the thermodynamics of C(sp)-H oxidative addition and kinetic influences upon regioselectivity are presented alongside pedagogically valuable experimental and computational results from the literature. Mechanisms and energetics of chelate-assisted C(sp)-H oxidative addition are examined, as are concepts related to chemoselectivity in the oxidative addition of C(sp)-H or C(sp)-X (X = F, Cl, Br, I) bonds with aryl halide substrates.

摘要

本文介绍了一个关于决定C(sp) - H活化和官能团化反应选择性的因素的教程，这些反应涉及与过渡金属的双电子氧化加成过程。文中阐述了C(sp) - H氧化加成的热力学与区域选择性动力学影响之间的相互作用，并结合了文献中具有教学价值的实验和计算结果。研究了螯合辅助的C(sp) - H氧化加成的机理和能量学，以及与芳基卤化物底物的C(sp) - H或C(sp) - X（X = F、Cl、Br、I）键氧化加成中的化学选择性相关的概念。

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