Organotin perfluorooctanesulfonates as air-stable Lewis acid catalysts: synthesis, characterization, and catalysis.
The reactions of 1,3-dichloro-1,1,3,3-tetrabutyldistannoxane and dialkyltin dihalides with silver perfluorooctanesulfonate provided the corresponding sulfonates as hydrates. The number of water molecules (n) of hydration was dependent on the conditions. The distannoxane derivative was identified as n from 0.5 to 6, while in the hydrated mononuclear species and DMSO complexes n varied widely from 4 to 13. 119Sn NMR spectroscopy and conductivity measurements indicated the ionic dissociation of these compounds in solution. These compounds exhibited unusually high solubility in polar organic solvents. The ionic dissociation together with facile hydration probably causes the unusual solubility. The Lewis acidity of these compounds was found to be high among organotin derivatives on the basis of ESR spectra of superoxide/metal-ion complexes. In contrast to well-known organotin triflates, these compounds suffered no hydrolysis upon storage in open air. The high catalytic activity of the distannoxane 1 was exemplified for various carbon-carbon bond-forming reactions, such as Mukaiyama-aldol as well as -Michael reactions and allylation of aldehydes.
An
De Lie
DL
Department of Chemistry, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China.
Peng
Zhihong
Z
Orita
Akihiro
A
Kurita
Akinobu
A
Man-e
Sumiyo
S
Ohkubo
Kei
K
Li
Xingshu
X
Fukuzumi
Shunichi
S
Otera
Junzo
J