Homogeneous Nickel Catalysts for the Selective Transfer of a Single Arylthio Group in the Catalytic Hydrothiolation of Alkynes

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• 作者：Denis A. Malyshev ; Natalie M. Scott ; Nicolas Marion ; Edwin D. Stevens ; Valentine P. Ananikov ; Irina P. Beletskaya ; Steven P. Nolan
• 刊名：Organometallics
• 出版年：2006
• 出版时间：September 11, 2006
• 年：2006
• 卷：25
• 期：19
• 页码：4462 - 4470
• 全文大小：206K
• 年卷期：v.25,no.19(September 11, 2006)
• ISSN：1520-6041

文摘

A novel homogeneous catalytic system has been developed for the regioselective hydrothiolation ofalkynes based on CpNi(NHC)Cl complexes (NHC = N-heterocyclic carbene). The designed catalystwas efficient for the selective addition of a single ArS group to an alkyne and was suitable for thesynthesis of vinylsulfides, without side reactions leading to bis(arylthio)alkenes. Furthermore, this catalyticsystem allowed for the S-H bond addition to alkynes to be performed with high regioselectivity (up to31:1) and in good yields (61-87%). A mechanistic study showed that this reaction involved three steps:(1) a nickel-based substitution of chloride for the ArS group, (2) alkyne insertion into the Ni-S bond,and (3) protonolysis of the Ni-C bond. The intermediate CpNi(NHC)(SAr) complexes were unambiguously characterized by X-ray analysis.