Organotin perfluorooctanesulfonates as air-stable Lewis acid catalysts: Synthesis, characterization, and catalysis

The reactions of 1,3-dichloro-1,1,3,3-tetrabutyldistannoxane and di-alkyltin dihalides with silver perfluoro-octanesulfonate 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 Inflates, these compounds suffered no hydrolysis upon storage in open air. The high catalytic activity of the distannoxane 1 was exemplified for various carboncarbon bond-forming reactions, such as Mukaiyama-aldol as well as -Michael reactions and allylation of aldehydes.