N,N,N',N'-Tetramethylethylenediamine → 3-Methoxyaniline

Participants

Reaction Steps

The advantageous effect of adding zinc chloride to an amination reaction was demonstrated in the amination reaction of 3-bromoanisole, the results of which are summarized in Table 10. When 3-bromoanisole was reacted under the standard lithium amide amination conditions, using lithium amide (10 eq.) in the presence of (CyPF-t-Bu)PdCl2 (1 mol %) in DME gave a complicated mixture of products was obtained (Table 10, Entry 1). When conducted in the presence of zinc chloride and TMEDA, however, the reaction could successfully gave the desired monoarylation product, 3-methoxyaniline, although at high concentrations N,N-dimethyl-3-methoxyaniline was formed in a significant amount as a by-product (Table 10, Entries 3 and 4). Under optimized conditions (Table 10, Entries 8 and 9), 3-methoxyaniline was formed selectively in good yield.

Provenance & Evidence