A DFT Computational Study on Electrophilic Substitutions upon α-Oxy-Substituted Benzylorganolithium Compounds:  Lithium Catalysis Is the Hidden Piece of the Puzzle

A detailed DFT (B3LYP/6-31+G*) study upon α-oxybenzylorganolithium compounds such as α-carbamoyloxybenzyllithium 1 has revealed two relevant issues concerning the outcome of electrophilic substitutions (1) lithium salts catalyze these reactions, and (2) some π lithium complexes can provide an extra position to which electrophiles can anchor and thus drive invertive (at the carbanionic carbon) processes. Calculations have shown that carboxylation, alkylation, and acylation should take place with inversion at the original C−Li bond.