A DFT computational study on electrophilic substitutions upon alpha-oxy-substituted benzylorganolithium compounds: lithium catalysis is the hidden piece of the puzzle.
A detailed DFT (B3LYP/6-31+G*) study upon alpha-oxybenzylorganolithium compounds such as alpha-carbamoyloxybenzyllithium 1 has revealed two relevant issues concerning the outcome of electrophilic substitutions (1) lithium salts catalyze these reactions, and (2) some pi 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.
Capó
Magdalena
M
Departamento de Química, Universidad de las Islas Baleares, 07122 Palma de Mallorca, Spain.
Saá
José M
JM