铜催化含氮和硫化物的乙烯基化反应研究(特邀稿件)有机化学.pdfVIP

DOI: 10.6023/cjoc1202082 综述与进展 有机化学 Chinese Journal of Organic Chemistry REVIEW 铜催化含氮和硫化物的乙烯基化反应研究 廖 骞 席婵娟* (清华大学化学系 北京 100084) 摘要 以铜为催化剂, 结合不同的反应条件, 分别阐述了酰胺、胺、唑类化合物和硫化物与卤代烯烃的交叉偶联反应, 从而分别得到了各种烯酰胺、烯胺、N-烯基唑类化合物和烯基硫醚化合物. 上述亲核试剂与 1,4-二卤-1,3-二烯化合物 反应, 经过两次乙烯基化反应, 可以高效地得到各种取代的吡咯和噻吩衍生物. 进一步阐述了 N—H 键以及其邻位 C—H 键也能够和 1,4-二卤-1,3-二烯反应, 生成唑并吡啶衍生物. 关键词 铜催化; N-乙烯基化; S-乙烯基化; N-双乙烯基化; S-双乙烯基化 Investigation on Copper-Catalyzed Vinylation of N- and S-Centered Nucleophiles Liao, Qian Xi, Chanjuan* (Department of Chemistry, Tsinghua University, Beijing 100084) Abstract Copper could be catalyst on the alkenylation reactions of amides, amines, azoles and sulfides, which afforded effi- cient methods for the synthesis of alkenylamides, enamines, alkenylazoles and alkenylsulfides. Under the conditions of the coupling processes, it would be possible to effect a related transformation as a means to access heterocycles in one-pot. Ac- cordingly, copper-catalyzed double alkenylations of amides, amines and sulfides to afford pyrroles and thiophenes have been expatiated. Furthermore, copper-catalyzed tandem alkenylations of azoles to afford nitrogen-bridgehead azolopyridine deriva- tives via an N—H bond and its adjacent C—H bond activation have been illustrated. Keywords copper-catalysis; N-vinylation; S-vinylation; N-double vinylation; S-double vinylation 近些年来, 随着金属有机化学的不断发展, 金属参 多, 反应选择性和产率也得到了很大改善. 如今, 铜催 与的有机反应得到了越来越广泛的研究和应用. 与传统 化的碳-杂原子