铑催化吲哚与乙烯基三乙氧基硅烷的C—H烯基化反应  

Rhodium⁃catalyzed C-H Alkenylation of Indoles and Vinyltriethoxysilane

作　　者：李鹏杰 周春妮 王泽田 郑子昂 张玉敏[1] 王亮[1] 肖标[1] LI Pengjie;ZHOU Chunni;WANG Zetian;ZHENG Ziang;ZHANG Yumin;WANG Liang;XIAO Biao(Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education,School of Chemical and Environmental Engineering,Jianghan University,Wuhan 430056,China)

机构地区：[1]江汉大学化学与环境工程学院,光电化学材料与器件教育部重点实验室,武汉430056

出　　处：《高等学校化学学报》2021年第8期2450-2457,共8页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21302064);湖北省自然科学基金(批准号:2017CFB690,2019CFB198)资助~。

摘　　要：研究了铑催化N-嘧啶吲哚与乙烯基三乙氧基硅烷的C—H烯基化反应.在以二氯(五甲基环戊二烯基)合铑(Ⅲ)二聚体{[RhCp^(*)Cl_(2)]_2(Cp^(*):五甲基环戊二烯基)}为催化剂,Cu(OAc)_(2)为氧化剂,Ag F为添加剂,1,2-二氯乙烷为溶剂及反应温度为90℃条件下,以42%~88%的收率得到末端吲哚乙烯衍生物.动力学同位素效应实验结果为K_(H)/K_(D)=5.7∶1,表明C—H键断裂可能是反应过程中的决速步骤.竞争性实验结果表明,含有供电子取代基的底物比吸电子取代基的底物反应活性高,反应可能经历亲电性C—H键活化过程.推测了可能的反应机理,主要包括配位、C—H键活化、转金属化、还原消除和氧化等步骤.将此方法应用于一种δ-咔啉衍生物的制备.A Rhodium-catalyzed direct C—H alkenylation of indoles using commercially available vinyltriethoxysilane as the vinylating reagent was developed.When the reaction was catalyzed by[RhCp*Cl_(2)]_(2) with Cu(OAc)_(2) as oxidant in the presence of AgF in 1,2-dichloroethane at 90℃,a series of terminal vinylindole derivatives could be obtained in 42%to 88%yields.The kinetic isotopic effect experiment was conducted and a KH/KD value of 5.7 was obtained,which suggested that the C—H bond cleavage was involved in the rate-determining step.The competition experiment between differently substituted indoles indicated that electron-rich indoles were preferentially converted,suggesting that an electrophilic C—H activation process might be involved in this transformation.A possible reaction mechanism,including coordination,C—H bond activation,transmetallization,reductive elimination and oxidantion,was then proposed.Moreover,this synthetic method was successfully applied to the synthesis ofδ-carboline derivative.

关 键 词：铑催化剂 C—H烯基化 吲哚 乙烯基三乙氧基硅烷 

分 类 号：O626.1[理学—有机化学]