Beilstein J. Org. Chem.2008,4, No. 13, doi:10.3762/bjoc.4.13
lithiation next to the OCF3 substituent is favoured, probably due to steric reasons. In fact, 1-trifluoromethoxy-4-(trifluoromethyl)benzene (Scheme 15) affords 2-trifluoromethoxy-5-(trifluoromethyl)benzoic acid after lithiation and carboxylation [75].
When the OCF3 substituent is in competition with fluorine
metalation with tert-butyllithium, followed by carboxylation (Scheme 20) [71]. When the amino function is protected instead of a BOC group by a silyl group, 3-trifluoromethoxy-N-(trimethylsilyl)aniline is metalated in position 2. However, 3- and 4-trifluoromethoxy-N,N-bis(trimethylsilyl)aniline are metalated