A highly regio- and stereo-selective hydrostannation reaction of various fluorine-containing internal acetylene derivatives

The hydrostannation reaction of various fluoroalkylated acetylene derivatives with tributyltin hydride was investigated using a variety of catalysts in toluene. Among them, the Et3B-induced hydrostannation reaction gave the highest regio- and stereo-selectivity. Their selectivity was mostly influenced upon the difference of the substituent X at the aromatic ring of the aryl-substituted internal acetylenes. Thus, the acetylenes having a halogen atom or an electron-donating group as X reacted smoothly with tributyltin hydride, affording the vinylstannane 4Z exclusively, while the acetylenes having an electron-withdrawing group (X = CO2Et, NO2) resulted in the preferential formation of 5E. The plausible mechanism of the formation of these products was discussed. (C) 2002 Elsevier Science B.V. All rights reserved.