Methods for Organic Electrosynthesis - Fundamentals and Applications of Organic Electrochemistry - page 62

reaction illustrated in Figure 4.2 can be shown
by the sequence CEC (pre-chemical reaction →
electrode process → follow-up chemical
reaction), and adsorption and desorption steps
are usually disregarded unless they are
important.
In order to clarify the reaction mechanism,
electrochemical analyses such as coulometry
and voltammetry in addition to ordinary
organic mechanistic studies are necessary to
obtain information such as the number of
electrons transferred, redox potentials and
detection of the reaction intermediates. The
details of the electrochemical analyses are
described in Chapters 2 and 3 .
4.3 Characteristics of Organic
Electrolytic Reactions
4.3.1 Umpolung
The polarity inversion of chemical bonding can
be readily carried out in electrolytic reactions
[6]. In other words, electrophiles can be
converted electrochemically to nucleophiles
without use of any reagents, and vice versa.
Such polarity inversion is widely used for
organic synthesis. For example, alkyl halides
are inherently electrophilic reagents. In order to
convert them to nucleophilic reagents, they
have to be transformed to Grignard reagents or
lithium compounds using Mg or Li metal.