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A Study of BF 3 ‐Promoted ortho Lithiation of Anilines and DFT Calculations on the Role of Fluorine–Lithium Interactions
Author(s) -
Kessar Satinder V.,
Singh Paramjit,
Singh Kamal N.,
Bharatam Prasad V.,
Sharma Arvind K.,
Lata Sneh,
Kaur Amarjit
Publication year - 2008
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.200705967
Subject(s) - metalation , lithium (medication) , fluorine , chemistry , medicinal chemistry , density functional theory , computational chemistry , group (periodic table) , inductive effect , organic chemistry , medicine , endocrinology
Director's cut : The poor directing ability of the dimethylamino group in directed ortho metalation is altered by complexation to BF 3 , which makes it more strongly activating than methoxy and chloro groups. DFT calculations of simplified lithiated intermediates reveal a small role of the inductive effect, but a distinctive F⋅⋅⋅Li interaction that leads to a F–Li distance which is remarkably similar to the C–Li distance.