乙二醇中钯催化无配体的室温Suzuki反应

篮化军2011Chinese Journal of catalysisVol 32 No. 7文章编号:02539837(2011)07120404DoI:10.3724SPJ088.2011.10225研究论文:1204~1207乙二醇中钯催化无配体的室温 Suzuki反应刘春,韩娜,袁浩,何晓宇,金子林大连理工大学精细化工国家重点实验室,辽宁大连116024摘要:报道了一种在室温下醋酸钯催化乙二醇中无外加配体的Suuk反应体系以K3PO47H2O为碱,在该体系中可高效进行芳基溴代物和芳基硼酸的 Suzuki交叉偶联反应,具有反应条件温和、无需惰性气体保护等特点.在n(ArBr)=0.5mmolm(ArB(OH)2)=0.75mmo,x(Pd(OAc)=05mol%,n(K3PO47H2O)=1.0mmo,y乙二醇)=2ml的优化条件下4溴苯甲醚和苯硼酸反应20min,分离收率即达95%关键词: Suzuki反应;钯;无配体;乙二醇;室温中图分类号:0643文献标识码:A收稿日期:201102-20.接受日期:2011-03-16.神通讯联系人.电话传真:(041)84986182;电子信箱:cliu@dlut.edu.cn基金来源:国家自然科学基金(21076034,20976024,20923060;中央高校基本科研业务费专项资金( DUTlILK5)Pd(OAc)r-Catalyzed Ligand-Free Suzuki Reaction in Ethylene glycolat room TemperatureLIU Chun, HAN Na, YUAN Hao, HE Xiaoyu, JIN ZilinState Key Laboratory of fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, ChinaAbstract: An aerobic and efficient protocol has been developed for the Pd(OAch-catalyzed ligand-free Suzuki reaction of aryl bromideswith aryl boronic acids in ethylene glycol at room temperature, affording cross-coupling products in good to excellent yields. Under the op-timized reaction conditions (i.e, 0.5 mmol ArBr, 0.75 mmol ArB(OHh, 0.5 mol% Pd(OAch, 1.0 mmol K, PO4 7H2O, and 2 ml ethyleneglycol). the Suzuki reaction between 4-bromoanisole and phenylboronic acid provided a 95% isolated yield in 20 min.Key words: Suzuki reaction; palladium; ligand-free; ethylene glycol; room temperatureReceived 20 February 2011. Accepted 16 March 2011*Correspondingauthor.Tel/Far:+86-411-84986182:E-mail:cliu@dlut.edu.cnThis work was supported by the National Natural Science Foundation of China(21076034, 20976024, 20923006)and the FundamentalResearch Funds for the Central Universities(DUTlILK15)Suz山交又偶联反应是现代有机合成中构建体等.但大多数配体存在合成困难,成本较高且CC键最为有效的方法之一-.它具有反应条件温和、有机硼试剂低毒和稳定性好、底物适用范围广eductivePa(o)oxidative等优点,已广泛应用于天然产物、医药、农药、除草addition剂、高分子传导材料和液晶材料等的合成16.目前Ar'-Pd(Il-Ar Ar-Pd(ll)-X公认的 Suzuki反应机理分为三个步骤,依次为氧化中国煤化工加成、金属转移化和还原消除8(见图式1),其中氧CNMHG化加成为反应决速步骤图式1钯催化的Suuk反应机理该反应通常需要添加膦配体或N杂环卡宾配Scheme 1. Mechanism of palladium-catalyzed Suzuki reaction.www.chxb.cn刘春等:乙二醇中钯催化无配体的室温 Suzuki反应1205对水和氧敏感,反应过程中需要溶剂除水和惰性气表1催化剂前体对4溴苯甲醚与苯硼酸 Suzuki I反应的影体保护等措施等问题,因而限制了它的应用.Pd催化无配体的反应体系因具有操作简单和成本低等优点Table 1 Effect of precatalysts on the Suzuki reaction4-bromoanisole and phenylboronic acid而备受关注16.目前,有机溶剂作为反应介质已广m·on-c