Methods for Organic Electrosynthesis - Fundamentals and Applications of Organic Electrochemistry - page 80

regioisomeric products. However, the
introduction of a silyl group as an
electroauxiliary directs the reaction pathway to
form a single product, as shown in Eq. 4.12
[22]. The silyl group also decreases the
oxidation potential of the amine.
(4.12)
4.5.2 Electroauxiliaries Based on
Readily Electron-Transferable
Functional Groups
Easily oxidizable functional groups like the
arylthio (ArS) group also work as
electroauxiliaries, i.e. the introduction of an ArS
group at the α position of ethers and
carbamates decreases their oxidation
potentials. Importantly, the oxidation of α-ArS
substituted heteroatom compounds results in
the selective cleavage of the C-S bond to
generate a cation intermediate stabilized by the
adjacent heteroatom. The resulting cation
intermediate reacts with a nucleophile to
provide the product selectively. The use of an
ArS group as an electroauxiliary expands the
scope of nucleophiles, which enables in situ use