DDQ/HNO_(3)/O_(2)催化的1,3-二芳基丙烯和1,3-二羰基化合物的交叉脱氢偶联反应研究  

The cross-dehydrogenative coupling of 1,3-diarylpropenes and 1,3-dicarbonyls catalyzed by DDQ/HNO_(3)/O_(2)

作　　者：程冬萍[1] 申静 蒲月琦 许孝良[2] CHENG Dongping;SHEN Jing;PU Yueqi;XU Xiaoliang(College of Pharmaceutical Science,Zhejiang University of Technology,Hangzhou 310014,China;College of Chemical Engineering,Zhejiang University of Technology,Hangzhou 310014,China)

机构地区：[1]浙江工业大学药学院,浙江杭州310014 [2]浙江工业大学化学工程学院,浙江杭州310014

出　　处：《浙江工业大学学报》2022年第3期318-327,共10页Journal of Zhejiang University of Technology

基　　金：浙江省自然科学基金资助项目(LY18B020018);国家自然科学基金资助项目(21602197)。

摘　　要：2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)是一种性能优良的有机氧化剂,广泛应用于脱氢芳构化、苄醚的脱保护、醇的氧化、氧化偶联、氧化成环等氧化反应。然而,超化学计量DDQ的使用带来的分离纯化困难、原子经济性低下等问题极大地限制了其在工业生产中的广泛应用。构建了以硝酸为电子转移媒介,氧气为终端氧化剂,DDQ为催化剂的催化氧化体系,研究了1,3-二芳基丙烯和1,3-二羰基化合物的交叉脱氢偶联反应,得到了一系列1,3-二羰基化合物烯丙基化的产物,收率为中等至良好。2,3-Dichloro-5,6-dicyano-1,4-benzoquinone(DDQ)is an organic oxidant with excellent performance,which is widely used in dehydroaromatization,deprotection of benzyl ether,oxidation of alcohol,oxidative coupling,oxidative cyclization and other oxidation reactions.However,large excess use of DDQ brings difficulties in product separation and purification and low atom economy,which greatly limits its wide applications.In this paper,we constructed a DDQ/HNO_(3)/O_(2)catalytic oxidation system with nitric acid as the electron transfer medium,oxygen as the terminal oxidant,and DDQ as the catalyst.The system can re-oxidize the reduction product DDQH_(2) of DDQ,effectively reducing the amount of DDQ,and achieving the cross-dehydrogenative coupling reaction of 1,3-diarylpropene and 1,3-dicarbonyl compounds.A series of allylated products of 1,3-dicarbonyl compounds with moderate to good yields.

关 键 词：2 3-二氯-5 6-二氰基-1 4-苯醌 硝酸 氧气 交叉脱氢偶联 

分 类 号：R914.5[医药卫生—药物化学]