90753-17-6Relevant articles and documents
Regioselective Homo- and Codimerization of 1-Alkynes Leading to 2,4-Disubstituted 1-Buten-3-ynes by Catalysis of a (η5-C5Me5)TiCl2/RMgX System
Akita, Munetaka,Yasuda, Hajime,Nakamura, Akira
, p. 480 - 487 (1984)
A series of 1-alkynes (RCCH where R=Et, n-Pr, n-Bu, n-C6H13, cyclohexyl, Ph, Me3Si, Me3SiCH2, and Me2SiOCH2) was found to dimerize regioselectively (>99percent) to 2,4-disubstituted 1-buten-3-ynes in 92-99percent yields by catalysis of (η5-C5Me
Selective Oligomerization and [2 + 2 + 2] Cycloaddition of Terminal Alkynes from Simple Actinide Precatalysts
Batrice, Rami J.,McKinven, Jamie,Arnold, Polly L.,Eisen, Moris S.
, p. 4039 - 4050 (2015/09/01)
A catalyzed conversion of terminal alkynes into dimers, trimers, and trisubstituted benzenes has been developed using the actinide amides U[N(SiMe3)2]3 (1) and [(Me3Si)2N]2An[κ2-(N,C)-CH2Si(CH3)N(SiMe3)] (An = U (2), Th (3)) as precatalysts. These complexes allow for preferential product formation according to the identity of the metal and the catalyst loading. While these complexes are known as valuable precursors for the preparation of various actinide complexes, this is the first demonstration of their use as catalysts for C-C bond forming reactions. At high uranium catalyst loading, the cycloaddition of the terminal alkyne is generally preferred, whereas at low loadings, linear oligomerization to form enynes is favored. The thorium metallacycle produces only organic enynes, suggesting the importance of the ability of uranium to form stabilizing interactions with arenes and related π-electron-containing intermediates. Kinetic, spectroscopic, and mechanistic data that inform the nature of the activation and catalytic cycle of these reactions are presented. (Chemical Equation Presented).
