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瞬态亚胺作为“下一代”导向基团,可在单次操作中催化官能化 C-H 键。

Transient imines as 'next generation' directing groups for the catalytic functionalisation of C-H bonds in a single operation.

机构信息

Department of Chemistry, Imperial College London, South Kensington, London, SW7 2AZ, UK.

出版信息

Org Biomol Chem. 2018 Jul 7;16(25):4582-4595. doi: 10.1039/c8ob00926k. Epub 2018 May 25.

Abstract

C-H functionalisation promises a paradigm shift in synthetic planning. However, the additional steps often required to install and remove directing groups currently detract from the efficiency. The strategy of reversible installation of a directing group via an imine linkage has recently emerged, with the imine formed and hydrolysed in situ. Such transient directing groups can promote transition metal catalysed functionalisation of unactivated C-H bonds of aldehydes, ketones and amines. This approach removes additional steps usually required for covalent directing groups and can use catalytic quantities of the imine forming component. This review updates the rapidly developing field of transient directing groups for C-H functionalisation on sp and sp carbon centres, to form new C-C and C-X bonds. We focus on the structures of the transient directing groups as mono or bidentate coordinating groups for various metal catalysts.

摘要

C-H 官能团化有望在合成规划中带来范式转变。然而,目前为了安装和去除导向基团通常需要额外的步骤,这降低了效率。最近出现了通过亚胺键可逆安装导向基团的策略,亚胺在原位形成并水解。这种瞬态导向基团可以促进过渡金属催化的醛、酮和胺的未活化 C-H 键的官能化。这种方法去除了通常需要共价导向基团的额外步骤,并可以使用催化量的亚胺形成组分。本综述更新了瞬态导向基团在 sp 和 sp 碳中心的 C-H 官能化领域的快速发展,以形成新的 C-C 和 C-X 键。我们专注于瞬态导向基团作为各种金属催化剂的单齿或双齿配位基团的结构。

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