银催化羧化偶联反应及钌催化交叉复分解反应串联合成官能团炔酸酯(英文)  

Sequential Ag‐catalyzed carboxylative coupling/Ru‐catalyzed cross‐metathesis reactions for the synthesis of functionalized 2‐alkynoates

作　　者：张琳琳[1] 张文珍[1] 石凌龙[1] 任祥[1] 吕小兵[1] 

机构地区：[1]大连理工大学精细化工国家重点实验室,辽宁大连116024

出　　处：《催化学报》2013年第6期1179-1186,共8页

基　　金：supported by the National Natural Science Foundation of China (20802007, 21111120073);the Fundamental Research Funds for the Central Universities (DUT12LK47);the Scientific Research Fund of Liaoning Provincial Education Department (L2012024)~~

摘　　要：通过将Ag催化的羧化偶联反应与Ru催化的交叉复分解反应串联,用端炔、二氧化碳、端烯基取代的溴代物和甲基丙烯酸甲酯高效高产率地合成了一系列官能团化的炔酸酯.Sequential reactions can provide efficient access to a variety of important organic compounds that would be otherwise difficult to obtain using conventional methods and readily available starting materials. Based on the importance of 2‐alkynoates in organic synthesis, the current research aimed to develop a method for the convenient synthesis of functionalized 2‐alkynoates from terminal alkynes, CO2 , terminal alkene‐derived bromides, and methyl acrylate using a combination of the carboxylative coupling and cross‐metathesis reactions. The initial ligand‐free silver‐catalyzed car‐ boxylative coupling reactions of a variety of different aryl‐substituted terminal alkynes and CO2 with 5‐bromopentene and 6‐bromohexene provided a series of 4‐pentenyl 2‐alkynoates and 5‐hexenyl 2‐alkynoates, respectively, in good yield. These resulting 2‐alkynoates were further transformed into methyl (E)‐6‐acetylenecarboxy‐2‐hexenoates and (E)‐7‐acetylenecarboxy‐2‐heptenoates in moderate to good yields by their cross‐metathesis reactions with methyl acrylate in the presence of the Grubbs‐Hoveyda catalyst. All of the new products characterized spectroscopically.

关 键 词：二氧化碳 羧化偶联反应 银催化剂 交叉复分解反应 Grubbs-Hoveyda催化剂 均相催化 

分 类 号：O621.3[理学—有机化学]