Aminoferrocene lithiation by boron trifluoride activation.

Lithiation of BF 3-complexed dimethylaminoferrocene occurs exclusively ortho to the dimethylamino group in the cyclopentadienyl ring providing structurally diverse products in 76-94% yield after electrophile quench. This method represents the first direct C2-lithiation of a monosubstituted aminoferrocene, offering rapid and complementary access to this class of compounds over procedures that utilize carbon- and sulfur-based directing groups and may serve as a prelude to an asymmetric process.