籃化軍2011Chinese Journal of catalysisVol 32 No. 7文章編號(hào):02539837(2011)07120404DoI:10.3724SPJ088.2011.10225研究論文:1204~1207乙二醇中鈀催化無配體的室溫 Suzuki反應(yīng)劉春,韓娜,袁浩,何曉宇,金子林大連理工大學(xué)精細(xì)化工國家重點(diǎn)實(shí)驗(yàn)室,遼寧大連116024摘要:報(bào)道了一種在室溫下醋酸鈀催化乙二醇中無外加配體的Suuk反應(yīng)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(yīng),具有反應(yīng)條件溫和、無需惰性氣體保護(hù)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(yīng)20min,分離收率即達(dá)95%關(guān)鍵詞: Suzuki反應(yīng);鈀;無配體;乙二醇;室溫中圖分類號(hào):0643文獻(xiàn)標(biāo)識(shí)碼:A收稿日期:201102-20.接受日期:2011-03-16.神通訊聯(lián)系人.電話傳真:(041)84986182;電子信箱:cliu@dlut.edu.cn基金來源:國家自然科學(xué)基金(21076034,20976024,20923060;中央高?；究蒲袠I(yè)務(wù)費(fèi)專項(xiàng)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(yīng)是現(xiàn)代有機(jī)合成中構(gòu)建體等.但大多數(shù)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(yīng)條件溫和、有機(jī)硼試劑低毒和穩(wěn)定性好、底物適用范圍廣eductivePa(o)oxidative等優(yōu)點(diǎn),已廣泛應(yīng)用于天然產(chǎn)物、醫(yī)藥、農(nóng)藥、除草addition劑、高分子傳導(dǎo)材料和液晶材料等的合成16.目前Ar'-Pd(Il-Ar Ar-Pd(ll)-X公認(rèn)的 Suzuki反應(yīng)機(jī)理分為三個(gè)步驟,依次為氧化中國煤化工加成、金屬轉(zhuǎn)移化和還原消除8(見圖式1),其中氧CNMHG化加成為反應(yīng)決速步驟圖式1鈀催化的Suuk反應(yīng)機(jī)理該反應(yīng)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:乙二醇中鈀催化無配體的室溫 Suzuki反應(yīng)1205對(duì)水和氧敏感,反應(yīng)過程中需要溶劑除水和惰性氣表1催化劑前體對(duì)4溴苯甲醚與苯硼酸 Suzuki I反應(yīng)的影體保護(hù)等措施等問題,因而限制了它的應(yīng)用.Pd催化無配體的反應(yīng)體系因具有操作簡單和成本低等優(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(jī)溶劑作為反應(yīng)介質(zhì)已廣m·on-c