德国哥廷根大学Lutz Ackermann团队报道了钴催化芳基C-H对映选择性电化学活化反应。相关研究成果发表在2023年3月10日出版的《科学》。

对映体选择性氧化还原转化通常依赖于昂贵的过渡金属作为催化剂，通常也需要化学计量量的化学氧化还原剂。电催化是一种更可持续的替代方法，特别是通过使用析氢反应（HER）代替化学氧化剂。

该文中，研究人员描述了使用钴代替贵金属催化剂进行不对称氧化的HER偶联对映体选择性芳基碳氢键（C–H）活化反应的策略。因此，实现了羧酸酰胺的高度对映选择性碳氢和氮氢（C–H和N–H）环化，从而获得了点手性和轴向手性化合物。此外，钴介导的电催化能够通过脱氢C–H活化反应选择性不对称制备各种磷（P）立体生成化合物。

附：英文原文

Title: Enantioselective electrochemical cobalt-catalyzed aryl C–H activation reactions

Author: Tristan von Münchow, Suman Dana, Yang Xu, Binbin Yuan, Lutz Ackermann

Issue&Volume: 2023-03-10

Abstract: Enantioselective redox transformations typically rely on costly transition metals as catalysts and often stoichiometric amounts of chemical redox agents as well. Electrocatalysis represents a more sustainable alternative, in particular through the use of the hydrogen evolution reaction (HER) in place of a chemical oxidant. In this work, we describe strategies for HER-coupled enantioselective aryl carbon-hydrogen bond (C–H) activation reactions using cobalt in place of a precious metal catalyst for the asymmetric oxidation. Thus, highly enantioselective carbon-hydrogen and nitrogen-hydrogen (C–H and N–H) annulations of carboxylic amides were achieved, which gave access to point and axially chiral compounds. Furthermore, the cobalt-mediated electrocatalysis enabled the preparation of various phosphorus (P)–stereogenic compounds by selective desymmetrization through dehydrogenative C–H activation reactions.

DOI: adg2866

Source: https://www.science.org/doi/10.1126/science.adg2866