乙二醇中鈀催化無(wú)配體的室溫Suzuki反應

籃化軍2011Chinese Journal of catalysisVol 32 No. 7文章編號:02539837(2011)07120404DoI:10.3724SPJ088.2011.10225研究論文:1204~1207乙二醇中鈀催化無(wú)配體的室溫 Suzuki反應劉春,韓娜,袁浩,何曉宇,金子林大連理工大學(xué)精細化工國家重點(diǎn)實(shí)驗室,遼寧大連116024摘要:報道了一種在室溫下醋酸鈀催化乙二醇中無(wú)外加配體的Suuk反應體系以K3PO47H2O為堿,在該體系中可高效進(jìn)行芳基溴代物和芳基硼酸的 Suzuki交叉偶聯(lián)反應,具有反應條件溫和、無(wú)需惰性氣體保護等特點(diǎn).在n(ArBr)=0.5mmolm(ArB(OH)2)=0.75mmo,x(Pd(OAc)=05mol%,n(K3PO47H2O)=1.0mmo,y乙二醇)=2ml的優(yōu)化條件下4溴苯甲醚和苯硼酸反應20min,分離收率即達95%關(guān)鍵詞: Suzuki反應;鈀;無(wú)配體;乙二醇;室溫中圖分類(lèi)號:0643文獻標識碼:A收稿日期:201102-20.接受日期:2011-03-16.神通訊聯(lián)系人.電話(huà)傳真:(041)84986182;電子信箱:cliu@dlut.edu.cn基金來(lái)源:國家自然科學(xué)基金(21076034,20976024,20923060;中央高?；究蒲袠I(yè)務(wù)費專(zhuān)項資金( 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山交又偶聯(lián)反應是現代有機合成中構建體等.但大多數配體存在合成困難,成本較高且CC鍵最為有效的方法之一-.它具有反應條件溫和、有機硼試劑低毒和穩定性好、底物適用范圍廣eductivePa(o)oxidative等優(yōu)點(diǎn),已廣泛應用于天然產(chǎn)物、醫藥、農藥、除草addition劑、高分子傳導材料和液晶材料等的合成16.目前Ar'-Pd(Il-Ar Ar-Pd(ll)-X公認的 Suzuki反應機理分為三個(gè)步驟,依次為氧化中國煤化工加成、金屬轉移化和還原消除8(見(jiàn)圖式1),其中氧CNMHG化加成為反應決速步驟圖式1鈀催化的Suuk反應機理該反應通常需要添加膦配體或N雜環(huán)卡賓配Scheme 1. Mechanism of palladium-catalyzed Suzuki reaction.www.chxb.cn劉春等:乙二醇中鈀催化無(wú)配體的室溫 Suzuki反應1205對水和氧敏感,反應過(guò)程中需要溶劑除水和惰性氣表1催化劑前體對4溴苯甲醚與苯硼酸 Suzuki I反應的影體保護等措施等問(wèn)題,因而限制了它的應用.Pd催化無(wú)配體的反應體系因具有操作簡(jiǎn)單和成本低等優(yōu)點(diǎn)Table 1 Effect of precatalysts on the Suzuki reaction4-bromoanisole and phenylboronic acid而備受關(guān)注16.目前,有機溶劑作為反應介質(zhì)已廣m·on-c