Methods for Organic Electrosynthesis - Fundamentals and Applications of Organic Electrochemistry - page 68

thermodynamically controlled. Since the
anodically generated radical cation
intermediate seems to be adsorbed on the
anode, deprotonation takes place preferentially
from a less hindered methyl group.
Consequently, this reaction is kinetically
controlled.

Figure 4.3 Regioselective anodic

methoxylation

In a similar manner, anodic methoxylation of
N -ethyl- N -methylaniline, the corresponding
carbamate, and amide derivatives also takes
place at the methyl group selectively ( Eq. 4.9 )
[9].

(4.9)

However, the regioselectivity can also be
explained by the difference in deprotonation
rates of radical cation intermediates (so-called
kinetic acidity [10]). For example, in the case of
anodic methoxylation of an aniline derivative