介孔ETS-10沸石担载Pd高效催化内炔氧化制备1,2-二酮  

Pd Supported on Mesoporous ETS-10 Zeolite Catalyst with Superior Catalytic Performances in Synthesizing 1,2-Diones from the Oxidation of Internal Alkynes

作　　者：刘长俊 胡慧玲 刘宬宏 朱超杰 唐天地[1] Liu Changjun;Hu Huiling;Liu Chenghong;Zhu Chaojie;Tang Tiandi(School of Petrochemical Engineering,Changzhou University,Changzhou,Jiangsu 213164;School of Chemistry and Chemical Engineering,Southeast University,Nanjing 211189)

机构地区：[1]常州大学石油化工学院,江苏常州213164 [2]东南大学化学化工学院,南京211189

出　　处：《有机化学》2023年第8期2953-2960,共8页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21776022,22178029)资助项目。

摘　　要：使用担载Pd的介孔ETS-10(Pd/METS-10)催化剂在清洁的反应条件下,实现了内炔氧化合成1,2-二酮类衍生物.研究发现,催化剂上高分散的Pd(Ⅱ)和炔烃配位形成电子受体供体复合物(EDX)是反应顺利进行的关键.随后二甲基亚砜(DMSO)亲核进攻生成的EDX,相继发生加成和消除反应,从而生成目的产物.Pd/METS-10催化的内炔氧化反应具有优异的产物选择性和好的底物范围,能够同时兼容对称/不对称内炔,且对底物的电子性质和立体效应不敏感.此外,Pd/METS-10催化剂在反应中表现出优异的重复性能,在循环使用5次后没有明显的活性损失.最后,根据表征结果和控制实验结果,提出了Pd/METS-10催化的内炔氧化制备1,2-二酮的反应机理.The 1,2-dione compounds was synthesized under clean reaction conditions over Pd/METS-10 catalyst.It has been found that the key step of the protocol is forming an electron donor-acceptor complex(EDX),as the coordination of Pd(II)and alkynyl.Then the nucleophilic addition and elimination reactions of dimethyl sulfoxide(DMSO)to the EDX were occurred,affording the target product.Pd/METS-10 catalyzed endo-acetylene oxidation possesses excellent product selectivity and good substrate scope.It is compatible with both symmetric and asymmetric endo-acetylene and is insensitive to the electronic properties and stereoscopic effects of the substrate.In addition,Pd/METS-10 catalyst showed excellent repetition performance in the reaction,with no significant loss of activity after five cycles.Finally,according to the characterization and control experiment results,the reaction mechanism of Pd/METS-10 catalyzed acetylene oxidation to produce 1,2-dione was proposed.

关 键 词：Pd/METS-10 内炔 1 2-二酮类衍生物 电子供体受体复合物 氧化反应 

分 类 号：O623.523[理学—有机化学] O621.251[理学—化学]