Liu Xian-Ming, Li Fu, Wang Tongkun, Dai Ling, Yang Yin, Jiang Neng-Quan, Xue Li-Yuan, Liu Jing-Yuan, Xue Xiao-Song, Xiao Li-Jun, Zhou Qi-Lin
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, China.
Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
J Am Chem Soc. 2025 Jan 8;147(1):627-635. doi: 10.1021/jacs.4c12544. Epub 2024 Dec 17.
The direct enantioselective functionalization of C(sp)-H bonds in organic molecules could fundamentally transform the synthesis of chiral molecules. In particular, the enantioselective oxidation of these bonds would dramatically change the production methods of chiral alcohols and esters, which are prevalent in natural products, pharmaceuticals, and fine chemicals. Remarkable advances have been made in the enantioselective construction of carbon-carbon and carbon-nitrogen bonds through the C(sp)-H bond functionalization. However, the direct enantioselective formation of carbon-oxygen bonds from C(sp)-H bonds remains a considerable challenge. We herein report a highly enantioselective C(sp)-H bond oxidative coupling with carboxylic acids. The method applies to allylic and propargylic C-H bonds and employs various carboxylic acids as oxygenating agents. The method successfully synthesized a range of chiral esters directly from readily available alkenes and alkynes, greatly simplifying the synthesis of chiral esters and related alcohols.
有机分子中C(sp) - H键的直接对映选择性官能团化可从根本上改变手性分子的合成。特别是，这些键的对映选择性氧化将极大地改变手性醇和酯的生产方法，而手性醇和酯在天然产物、药物和精细化学品中很常见。通过C(sp) - H键官能团化在对映选择性构建碳 - 碳键和碳 - 氮键方面取得了显著进展。然而，由C(sp) - H键直接对映选择性形成碳 - 氧键仍然是一个巨大的挑战。我们在此报告了一种与羧酸的高度对映选择性C(sp) - H键氧化偶联反应。该方法适用于烯丙基和炔丙基C - H键，并使用各种羧酸作为氧化试剂。该方法成功地直接从易得的烯烃和炔烃合成了一系列手性酯，极大地简化了手性酯及相关醇的合成。
