Wang Qiang, Ruan Zi-Sheng, Wang Hong-Peng, Liang Ren-Xiao, Hu Yuan-Yuan, Jia Yi-Xia
College of Chemical Engineering, State Key Laboratory Breeding Base of Green Chemical Synthesis Technology, Zhejiang University of Technology, Chaowang Road 18#, Hangzhou 310014, P. R. China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China.
J Org Chem. 2024 Dec 6;89(23):17133-17140. doi: 10.1021/acs.joc.4c01488. Epub 2024 Nov 19.
Herein, a cobalt-catalyzed intramolecular enantioselective reductive Heck reaction is disclosed. Starting from --iodoaryl-2-(trifluoromethyl)acrylamides, a plethora of chiral oxindoles bearing trifluoromethylated quaternary stereogenic centers at the C3-position are achieved in moderate to good yields (up to 88% yield) and good to excellent enantioselectivities (up to 94% ee) by employing zinc/silane as reducing agent. Other than the trifluoromethyl group, a number of chiral oxindoles bearing alkyl, aryl, and ester groups at C3-position were also obtained albeit in relatively lower enantioselectivities (68-78% ee).
在此，我们报道了一种钴催化的分子内对映选择性还原Heck反应。以碘代芳基-2-(三氟甲基)丙烯酰胺为起始原料，通过使用锌/硅烷作为还原剂，以中等至良好的产率（高达88%）和良好至优异的对映选择性（高达94% ee）得到了大量在C3位带有三氟甲基化季碳立体中心的手性氧化吲哚。除了三氟甲基外，还获得了一些在C3位带有烷基、芳基和酯基的手性氧化吲哚，尽管其对映选择性相对较低（68 - 78% ee）。
