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Controlling Chemoselectivity in the Lithiation of Substituted Aromatic Tertiary Amides
Author(s) -
Armstrong David R.,
Boss Sally R.,
Clayden Jonathan,
Haigh Robert,
Kirmani Basel A.,
Linton David J.,
Schooler Paul,
Wheatley Andrew E. H.
Publication year - 2004
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200353324
Subject(s) - chemoselectivity , chemistry , regioselectivity , density functional theory , dimer , benzamide , lewis acids and bases , monomer , medicinal chemistry , solvent , solvation , organic chemistry , computational chemistry , catalysis , polymer
Solvent effects control the regioselectivity with which tert ‐butyllithium deprotonates 2‐ethyl‐ N , N ‐diisopropyl‐1‐benzamide. From THF an ortho ‐lithiated dimer is isolated but from N , N , N ′, N ′′, N ′′pentamethyldiethylenetriamine (pmdeta) a laterally lithiated monomer is obtained (see scheme). Density functional theory (DFT) calculations point to the importance of Lewis base solvation and aggregation state in determining the chemoselectivity.