Anisole reaction with organolithium

The above comments should not be taken as claims that anisole and diphenyl ether cannot be metallated by organolithium species. For example, alkyllithiums are known (38,39,40) to react with anisole, usually in the ortho position. However, these reactions are generally slow, particularly at ambient temperature and when the ether is diluted with a hydrocarbon solvent. Our results merely indicate that active center deactivation via metallation of these aromatic ethers is not a serious problem during the time span of our measurements with species that are, at least, partially delocalized (33J ... 

A(-(Arylthiomethyl)amines, which are easily prepared and reportedly have better shelf stability than the corresponding )V-(alkoxymethyl)amines, have also been utilized to prepare tertiary amines. Alkenyl cuprate addition to )V,A -diethylphenylthiomethylamine produces allylic amines in high yield (entry 1, Table 6). Both alkenyl groups of the cuprate react. 5-(Dialkylaminomethyl) dithiocarbamates (entry 2, Table 6), sulfonates (entry 3, Table 6) and amides also generate iminium salts in situ. Of a variety of amides examined, imides such as dialkylaminomethyl-succinimides (entry 4, Table 6) and -phthali-mides provide the best overall yields. Organolithium reagents are rarely utilized in aminomethylation reactions. However, )V-chloromethylamines condense readily with lithiated anisole derivatives (entry S, Table 6). ... 

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