Chemoselectivity in the Kosugi-Migita-Stille coupling of bromophenyl triflates and bromo-nitrophenyl triflates with (ethenyl)tributyltin

Kosugi-Migita-Stille cross coupling reactions of (ethenyl)tributyltin with all isomeric permutations of bromophenyl triflate and bromo-nitrophenyl triflate were examined in order to determine the chemoselectivity of carbon-bromine versus carbon-triflate bond coupling under different reaction conditions. In general, highly selective carbon-bromine bond cross couplings were observed using for example bis(triphenylphosphine)palladium dichloride (2 mol-%) in 1,4-dioxane at reflux. In contrast, reactions using the same pre-catalyst but in the presence of a three-fold excess of lithium chloride in N,N-dimethylformamide at ambient temperature were in most cases selective for coupling at the carbon-triflate bond. Overall, isolated yields and the selectivity for carbon-bromine bond coupling were significantly higher compared to carbon-triflate bond coupling. [Display omitted]