Formation of vinylidenes from internal alkynes at a cyclotriphosphato ruthenium complex.
A ruthenium cyclotriphosphato (P(3)O(9)(3-)) 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.
Ikeda
Yousuke
Y
Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan.
Yamaguchi
Takafumi
T
Kanao
Keiichiro
K
Kimura
Kazuhiro
K
Kamimura
Sou
S
Mutoh
Yuichiro
Y
Tanabe
Yoshiaki
Y
Ishii
Youichi
Y