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A study on the metalation of fluorinated phenyl benzyl ethers
Author(s) -
Kliś Tomasz,
Serwatowski Janusz,
Wójcik Dominik
Publication year - 2006
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.1107
Subject(s) - chemistry , metalation , fluorine , inductive effect , aryl , ring (chemistry) , butyllithium , yield (engineering) , medicinal chemistry , lithium atom , lithium (medication) , oxygen atom , oxygen , organic chemistry , molecule , ion , alkyl , medicine , materials science , metallurgy , ionization , endocrinology
Lithiation of a series of aryl benzyl ethers containing fluorine atoms or CF 3 −group in the phenolic ring has been studied. It was found that the long‐distance inductive effect (two fluorine atoms in 2,6‐ or 2,3‐position to the oxygen) and the cooperation of the coordination and inductive effects (fluorine atom or CF 3 −group meta to oxygen atom) are the main factors directing ortho lithiation. Dilithiation of aryl benzyl ethers by butyllithium is generally less effective, but in the presence of PMDTA occurs efficiently and gives compounds containing lithium atoms at the phenyl ring and in the benzylic position. 2,3‐Difluoro‐benzyloxybenzene was dilithiated using BuLi–PMDTA complex and the intermediate was trapped with Me 3 SiCl to give disilylated product in high yield. Copyright © 2006 John Wiley & Sons, Ltd.