Preparation of 2,2-difluoro-1-trialkylsilylethenylstannanes and their cross-coupling reactions

Reaction of 2 with bis(tributyltin) in the presence of 3 mol % Pd2(dba)3, 6 mol % XPhos, and 30 equiv of LiBr in wet and air bubbled THF at reflux for 8 h afforded the desired products 3 in 73-74% yields. The cross-coupling reaction of 3a with aryl iodides in the presence of 10 mol % Pd(PPh3)4 and 10 mol % CuI afforded the coupled products 4a-p in 47-90% yields. The coupling reaction of 3b with various alkynyl bromides having aryl-, alkyl, or trialkylsilyl group also afforded the corresponding 1,3-enynes 5a-g in 61-77% yields.