华南理工大学黄良斌研究团队报道了Rh(III)催化(均)烯丙基硫化物的非对映和对映选择性区域发散(异)芳基酰胺化。相关研究成果发表在2024年3月28日出版的《美国化学会杂志》。

研究报道了铑催化的（均）烯丙基硫化物、有机硼酸和二恶唑酮的3-组分结合，非对映和区域选择性芳基酰胺化反应。这些反应分别产生烯丙基硫化物和高烯丙基硫化物的1,2-插入和2,1-插入芳基酰胺化产物。

研究实现了末端和内部烯丙基硫化物的对映选择性芳基酰胺化，以高产率提供了具有一个或两个连续立体中心的各种1,3-N，S化合物，并具有高的非对映选择性和对映选择性。机理研究表明，天然和易于去除的硫化物基团引起的周转限制和选择性决定步骤发生了变化。

附：英文原文

Title: Rh(III)-Catalyzed Diastereo- and Enantioselective Regiodivergent (Hetero)Arylamidation of (Homo)Allylic Sulfides

Author: Xiaoyan Jia, Gui-Lin Hao, Mengxia Feng, Huanfeng Jiang, Shou-Guo Wang, Liangbin Huang

Issue&Volume: March 28, 2024

Abstract: A rhodium-catalyzed 3-component conjunctive diastereo- and regioselective arylamidation of (homo)allylic sulfides, organon boronic acids, and dioxazolones is reported. These reactions deliver the 1,2-insertion and 2,1-insertion arylamidation products, respectively, for allylic sulfides and homoallylic sulfides. The enantioselective arylamidation of terminal and internal allylic sulfides is achieved, furnishing various 1,3-N,S compounds featuring one or two contiguous stereocenters in high yields and with high diastereo- and enantioselectivities. Mechanistic studies suggest a change in the turnover-limiting and selectivity-determining steps induced by the native and easily removable sulfide group.

DOI: 10.1021/jacs.3c14041

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.3c14041