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

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...

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Veröffentlicht in:Journal of the American Chemical Society 2004-12, Vol.126 (51), p.16738-16739
Hauptverfasser: CAPO, Magdalena, SAA, José M
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Chemistry
Exact sciences and technology
Kinetics and mechanisms
Organic chemistry
Reactivity and mechanisms
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container_issue 51
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container_title Journal of the American Chemical Society
container_volume 126
creator CAPO, Magdalena
SAA, José M
description 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.
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Exact sciences and technology
Kinetics and mechanisms
Organic chemistry
Reactivity and mechanisms
title A DFT Computational Study on Electrophilic Substitutions upon α-Oxy-Substituted Benzylorganolithium Compounds:  Lithium Catalysis Is the Hidden Piece of the Puzzle
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