TMSCH(2)Li and TMSCH(2)Li-LiDMAE: efficient reagents for noncryogenic halogen-lithium exchange in bromopyridines

TMSCH(2)Li and TMSCH(2)Li-LiDMAE have been used efficiently for bromine-lithium exchange in 2-bromo-, 3-bromo-, and 2,5-dibromopyridines under noncryogenic conditions, while low temperatures (-78 to -100 degrees C) are always needed with n-BuLi. The aminoalkoxide LiDMAE induced a remarkable C-2 selectivity with 2,5-dibromopyridines in toluene at 0 degrees C, which was unprecedented at such a temperature. The lithiopyridines were successfully reacted with electrophiles also under noncryogenic conditions giving the expected adducts in good yields.