Formation of Vinylidenes from Internal Alkynes at a Cyclotriphosphato Ruthenium Complex

被引：71

作者：

Ikeda, Yousuke ^{[1
]}

Yamaguchi, Takafumi ^{[1
]}

Kanao, Keiichiro ^{[1
]}

Kimura, Kazuhiro ^{[1
]}

Kamimura, Sou ^{[1
]}

Mutoh, Yuichiro ^{[1
]}

Tanabe, Yoshiaki ^{[1
]}

Ishii, Youichi ^{[1
]}

机构：

[1] Chuo Univ, Fac Sci & Engn, Dept Appl Chem, Bunkyo Ku, Tokyo 1128551, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2008年 / 130卷 / 50期

关键词：

D O I：

10.1021/ja8080567

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A ruthenium cyclotriphosphato (P3O93-) complex with a labile MeOH ligand can affect the vinylidene rearrangement of general internal alkynes via the 1,2-migration of alkyl, aryl, and acyl groups. This provides the first internal alkyne-to-vinylidene isomerization with high generality. Several intermediary eta(2)-alkyne complexes could be isolated and were successfully transformed into the corresponding vinylidene complexes. The reaction mechanism is also discussed on the basis of a kinetic study and migratory aptitude of alkyl., aryl, and acyl groups; the present reaction proceeds via an intramolecular process and is viewed as an uncommon electrophilic rearrangement.

引用

页码：16856 / +

页数：3

共 34 条

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