文献类型：期刊文献

英文题名：Selective Formation of 1,4-Disubstituted Triazoles from Ruthenium-Catalyzed Cycloaddition of Terminal Alkynes and Organic Azides: Scope and Reaction Mechanism

作者：Liu, Pei Nian[2,3,4];Li, Juan[2];Su, Fu Hai[2];Ju, Kun Dong[3,4];Zhang, Li[2];Shi, Chuan[2];Sung, Herman H. Y.[2];Williams, Ian D.[2];Fokin, Valery V.[1];Lin, Zhenyang[2];Jia, Guochen[2]

机构：[1]Scripps Res Inst, La Jolla, CA 92037 USA;[2]Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China;[3]E China Univ Sci & Technol, Shanghai Key Lab Funct Mat Chem, Shanghai 200237, Peoples R China;[4]E China Univ Sci & Technol, Inst Fine Chem, Shanghai 200237, Peoples R China

年份：2012

卷号：31

期号：13

起止页码：4904

外文期刊名：ORGANOMETALLICS

收录：;EI(收录号：20122915253417);WOS:【SCI-EXPANDED(收录号:WOS:000306149300040)】；

基金：This work was supported by the Hong Kong Research Grant Council (Project Nos. HKUST 601306, HKUST 601408, and HKU1/CRF/08), the National Natural Science Foundation of China (Project Nos. 21172069 and 21190033), the Innovation Program of Shanghai Municipal Education Commission (Project No. 12ZZ050), and the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Catalysis - Catalyst activity - Ruthenium compounds - Hydrocarbons

摘要：The catalytic activity of a series of ruthenium complexes lacking cyclopentadienyl ligands has been evaluated for the cycloaddition of terminal alkynes and azides to give selectively 1,4-disubstituted 1,2,3-triazoles. The complex RuH(eta(2)-BH4)(CO)(PCy3)(2) was found to be an effective catalyst for the cycloaddition reactions. In the presence of RuH(eta(2)-BH4)(CO)(PCy3)(2), primary and secondary azides reacted with a range of terminal alkynes containing various functionalities to selectively produce 1,4-disubstituted 1,2,3-triazoles. The ruthenium-catalyzed azide-alkyne cycloaddition appears to proceed via a Ru-acetylide species as the key intermediate, which undergoes formal cycloaddition with an azide to give a ruthenium triazolide complex. The 1,4-disubstituted 1,2,3-triazole product is generated by metathesis of the triazolide complex with a terminal alkyne. In support of the reaction mechanism, the acetylide complex Ru(C CCMe3)(2)(CO)(PPh3)(3) reacts cleanly with benzyl azide to give a ruthenium triazolide complex, which reacts with excess tert-butylacetylene in the presence of PPh3 to give 4-tert-butyl-1-benzyl-1,2,3-triazole and the diacetylide complex Ru(C CCMe3)(2)(CO)(PPh3)(3). The mechanism is also supported by DFT calculations.