Qi Xu-Kuan, Dai Qiang, Gu Yangyi, Lau Kwan Shing, Sung Herman H Y, Williams Ian D, Lin Zhenyang, Zhang Chaoshen, Sun Jianwei
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon 999077, Hong Kong SAR, China.
State Key Laboratory of Microbial Technology, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
J Am Chem Soc. 2025 Jun 18;147(24):20225-20232. doi: 10.1021/jacs.5c06136. Epub 2025 Jun 9.
Although the copper-catalyzed allylic C(sp)-H oxygenation (Kharasch-Sosnovsky reaction) is a powerful transformation known for over a half century, its enantioselective version has been developed with drawbacks. High enantioselectivity was not achieved for acyclic terminal olefins and tertiary C-H bonds. Here we have addressed these long-standing challenges enabled by the design of new SphenBOX ligands. When combined with photocatalysis, a range of valuable allylic esters can be obtained directly from terminal olefins and carboxylic acids with high efficiency, regioselectivity, and enantioselectivity. Unprecedented enantioconvergent oxygenation of allylic tertiary C(sp)-H bonds is demonstrated, allowing construction of quaternary stereocenters with high enantioselectivity. Structural analysis indicates that SphenBOX features a compact chiral pocket that may contribute to its superior performance.
尽管铜催化的烯丙基C(sp)-H氧化反应（卡拉施-索斯诺夫斯基反应）是一项已为人所知半个多世纪的强大转化反应，但其对映选择性版本的开发存在缺陷。对于无环端烯和叔C-H键，尚未实现高对映选择性。在此，我们通过设计新型SphenBOX配体解决了这些长期存在的挑战。当与光催化相结合时，一系列有价值的烯丙基酯可直接从端烯和羧酸中高效、区域选择性和对映选择性地获得。烯丙基叔C(sp)-H键前所未有的对映汇聚式氧化反应得以证明，从而能够以高对映选择性构建季碳立体中心。结构分析表明，SphenBOX具有一个紧凑的手性口袋，这可能有助于其卓越性能。
