铜催化亚甲基环丙烷的1,3-二硼化反应  

Copper-catalyzed 1,3-Diborylation of Alkylidenecyclopropanes

作　　者：刘朋瑞 纪苗苗 杨蕤林 刘屹 马爱军 彭金宝 LIU Pengrui;JI Miaomiao;YANG Ruilin;LIU Yi;MA Aijun;PENG Jinbao(School of Pharmacy and Food Engineering,Wuyi University,Jiangmen 529020,China)

机构地区：[1]五邑大学药学与食品工程学院,广东江门529020

出　　处：《合成化学》2024年第12期1028-1034,共7页Chinese Journal of Synthetic Chemistry

基　　金：五邑大学高层次人才科研启动项目(2018TP018)。

摘　　要：有机合成中二硼化合物被广泛应用于药物合成及材料化学,因此,合成该类化合物的方法一直倍受关注。本文研究了铜催化下亚甲基环丙烷(ACPs)与亚甲基环丙烷(ACPs)反应合成1,3-二硼化合物的反应。在廉价过渡金属铜的催化下,以联硼酸频那醇酯(B_(2)pin_(2))为硼源,甲醇锂为碱,1,1′-联萘-2,2′-双二苯膦(BINAP)为配体,90℃反应20 h,首次合成一系列近端开环的1,3-二硼化合物(3a~3i)。该反应体系可兼容不同类型的取代基(甲氧基、甲硫基、三氟甲基和苄氧基)以及苯并氧杂环类底物,能以63%~71%的收率得到目标产物。产物结构经^(1)H NMR、^(13)C NMR和HR-MS(ESI)表征。Diboron compounds are widely used in organic synthesis,and the methods for the synthesis of such compounds have always attracted much attention.This work studied the synthesis of 1,3-diboron compounds via copper catalyzed reaction of alkylidenecyclopropanes(ACPs).A series of proximal open-ring 1,3-diboron compounds(3a~3i)were synthesized using IMesCuCl as the catalyst,pinacol diborate(B_(2)pin_(2))as the boron source,and lithium methoxide as the base,1,1′-binaphthyl-2,2′-bisdiphenylphosphine as the ligand.This reaction system is compatible with different substituents(methoxy,methylthio,trifluoromethyl and benzyloxy)and benzox hetercyclic substrates.The structure of the products was characterized by ^(1)H NMR,^(13)C NMR and HR-MS(ESI).

关 键 词：铜催化 亚甲基环丙烷类化合物 加成反应 开环反应 二硼类化合物 

分 类 号：O62[理学—有机化学]