Coupling of terminal alkynes and isonitriles by organoactinide complexes: Scope and mechanistic insights

被引：33

作者：

Barnea, Eyal ^{[1
,2
]}

Andrea, Tamer ^{[1
,2
]}

Berthet, Jean-Claude ^{[3
]}

Ephritikhine, Michel ^{[3
]}

Eisen, Moris S. ^{[1
,2
]}

机构：

[1] Technion Israel Inst Technol, Schulich Fac Chem, IL-32000 Haifa, Israel

[2] Technion Israel Inst Technol, Inst Catalysis Sci & Technol, IL-32000 Haifa, Israel

[3] CEA Saclay, CNRS, Lab Claude Frejacques, Serv Chim Mol,DSM IRAMIS,URA 331, F-91191 Gif Sur Yvette, France

来源：

ORGANOMETALLICS | 2008年 / 27卷 / 13期

关键词：

D O I：

10.1021/om701223x

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The coupling reaction of terminal alkynes with several isonitriles, catalyzed by the neutral organoactinide complexes CP*(2)AnMe(2) (CP* = C5Me5, An = Th, U) or the cationic complex [(Et2N)(3)U][BPh4], yielded substituted alpha,beta-acetylenic aldimines, in good to excellent yields. The reaction proceeded via a 1,1-insertion of the isonitrile carbon into a metal-acetylide bond, followed by a protonolysis by the acidic proton of the terminal alkyne. Additional insertion products were obtained by altering the catalyst and the reactant ratios. A plausible mechanism for the catalytic reaction is also presented, based on kinetics measurements and thermodynamic studies of the coupling reaction with CP*2ThMe2 or [(Et2N)(3)U][BPh4] as catalysts. The reaction is first-order in catalyst and isonitrile and zero-order in alkyne.

引用

页码：3103 / 3112

页数：10

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