Mechanistic investigation of the Ru-catalyzed hydroamidation of terminal alkynes.

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作者：

M Arndt，KSM Salih，A Fromm，LJ Goossen，F Menges，G Niedner-Schatteburg

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摘要：

The ruthenium-catalyzed hydroamidation of terminal alkynes has evolved to become a broadly applicable tool for the synthesis of enamides and enimides. Depending on the catalyst system employed, the reaction leads chemo-, regio-, and stereoselectively to a single diastereoisomer. Herein, we present a comprehensive mechanistic study of the ruthenium-catalyzed hydroamidation of terminal alkynes, which includes deuterium-labeling, in situ IR, in situ NMR, and in situ ESI-MS experiments complemented by computational studies. The results support the involvement of ruthenium-hydride and ruthenium-vinylidene species as the key intermediates. They are best explained by a reaction pathway that consists of an oxidative addition of the amide, followed by insertion of a π-coordinated alkyne into a ruthenium-hydride bond, rearrangement to a vinylidene species, nucleophilic attack of the amide, and finally reductive elimination of the product.

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关键词：

Mg-Al-RE alloy Al11RE3 Thermal stability Mechanical properties

DOI：

10.1021/ja111389r

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年份：

2011