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配体控制的 NiH 催化的烯烃区域选择性链行走氢烷基化反应。

Ligand-Controlled NiH-Catalyzed Regiodivergent Chain-Walking Hydroalkylation of Alkenes.

机构信息

Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, Tianjin, 300387, P. R. China.

State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.

出版信息

Angew Chem Int Ed Engl. 2022 Jul 25;61(30):e202204716. doi: 10.1002/anie.202204716. Epub 2022 Jun 8.

DOI:10.1002/anie.202204716
PMID:35608276
Abstract

A NiH-catalyzed migratory hydroalkylation of alkenyl amines with predictable and switchable regioselectivity is reported. By utilizing a ligand-controlled, directing group-assisted strategy, various alkyl units are site-selectively installed at inert sp C-H sites far away from the original C=C bonds. A range of structurally diverse α- and β-branched protected amines are conveniently synthesized via stabilization of 5- and 6-membered nickelacycles respectively. This method exhibits broad scope and high functional group tolerance, and can be applied to late-stage modification of medicinally relevant molecules.

摘要

报道了一种 NiH 催化的烯基胺的 migratory hydroalkylation,具有可预测和可切换的区域选择性。通过利用配体控制、导向基团辅助的策略,各种烷基单元可以在远离原始 C=C 键的惰性 sp C-H 位点上选择性地安装。通过分别稳定 5-和 6 元镍环,方便地合成了一系列结构多样的α-和β-支链保护胺。该方法具有广泛的适用范围和高的官能团容忍度,可以应用于药物相关分子的后期修饰。

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