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A Computational Study of the Intramolecular Carbolithiation of Aryllithiums: Solvent and Substituent Effects
Author(s) -
Mattalia JeanMarc,
Nava Paola
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201501208
Subject(s) - substituent , intramolecular force , solvent , chemistry , computational chemistry , solvent effects , double bond , stereochemistry , organic chemistry
The intramolecular carbolithiation of olefinic aryllithiums provides an interesting route to functionalized carbo‐ and heterocyclic systems. We have computed mechanistic energy profiles (DFT) by varying the nature of the solvent and aryllithium. Our calculations suggest that the solvent mainly impacts the aggregation state of the aryllithium intermediates rather than activates the reactive species themselves. Further investigations revealed that substitution of the terminal position of the double bond and the N ‐allyl side‐chain strongly influence the energy barriers, in good agreement with experimental data.