南方科技大学刘心元团队报道了Cu催化的对映选择性自由基杂原子S–O交叉偶联。相关研究成果于2022年12月27日发表在国际顶尖学术期刊《自然化学》。

过渡金属催化的交叉偶联反应已成为以外消旋和对映选择性方式高效构建碳-碳/杂原子（除碳以外的p-嵌段元素）键的最可靠和实用的合成工具之一。相比之下，迄今为止，相应的杂原子-杂原子交叉偶联的发展仍然难以实现，这可能是由于对杂原子-杂原子的还原消除研究不足且经常面临挑战。

该文中，研究人员基于实验和理论结果，证明了单电子还原消除作为在铜催化下发展对映选择性S–O偶联的策略。该反应通过快速制备具有挑战性的手性醇（具有密集的立体中心）、生物质衍生原料甘油的适宜稳定化以及肌醇的显著催化4,6-去对称化显示了其合成潜力。研究结果证明了对映选择性自由基-杂原子交叉偶联作为一般手性杂原子-杂原子形成策略的潜力。

附：英文原文

Title: Cu-catalysed enantioselective radical heteroatomic S–O cross-coupling

Author: Cheng, Yong-Feng, Yu, Zhang-Long, Tian, Yu, Liu, Ji-Ren, Wen, Han-Tao, Jiang, Na-Chuan, Bian, Jun-Qian, Xu, Guo-Xiong, Xu, Dan-Tong, Li, Zhong-Liang, Gu, Qiang-Shuai, Hong, Xin, Liu, Xin-Yuan

Issue&Volume: 2022-12-27

Abstract: The transition-metal-catalysed cross-coupling reaction has established itself as one of the most reliable and practical synthetic tools for the efficient construction of carbon–carbon/heteroatom (p-block elements other than carbon) bonds in both racemic and enantioselective manners. In contrast, development of the corresponding heteroatom–heteroatom cross-couplings has so far remained elusive, probably due to the under-investigated and often challenging heteroatom–heteroatom reductive elimination. Here we demonstrate the use of single-electron reductive elimination as a strategy for developing enantioselective S–O coupling under Cu catalysis, based on both experimental and theoretical results. The reaction manifests its synthetic potential by the ready preparation of challenging chiral alcohols featuring congested stereocentres, the expedient valorization of the biomass-derived feedstock glycerol, and the remarkable catalytic 4,6-desymmetrization of inositol. These results demonstrate the potential of enantioselective radical heteroatomic cross-coupling as a general chiral heteroatom–heteroatom formation strategy.

DOI: 10.1038/s41557-022-01102-z

Source: https://www.nature.com/articles/s41557-022-01102-z