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B
ecause electrochemistry
allows for the selective intro-
duction and removal of elec-
trons from organic molecules,
it is an ideal tool for reversing
the polarity of known functional
groups and triggering umpolung reac-
tions. For example, electrons can be
added to electron-poor functional
groups in order to convert them from
electrophiles into nucleophiles or
removed from electron-rich functional
groups in order to convert them from
nucleophiles into electrophiles (Fig. 1).
The ensuing reactive intermediates can
then be trapped in order to complete
reactions that involve the net coupling
FIG. 1. Electrons can be added to electron-poor functional groups in order to convert them from electrophiles
of either two electrophiles or two nucle-
into nucleophiles or removed from electron-rich functional groups in order to convert them from nucleophiles
ophiles in ways that would be other- into electrophiles.
wise impossible. Such reactions are
intriguing because their availability cre-
ates the potential for developing entire- blocks. Each scheme is organized with nucleophilic addition to a carbonyl
ly new synthetic strategies for the con- the radical anion at the center, while the group, and to achieve asymmetric induc-
struction of complex molecules. What array of accessible functionality is dis- tion (Fig. 3, example (g)).10 Nitroalkenes
follows is a short (non-comprehensive) played around the perimeter. The cou- can also serve as substrates.11 When
review of recent developments that pling partner is indicated in parenthesis. reduced, the radical anion participates in
point the way to what can be accom- New bonds are highlighted in blue. A two different reaction pathways,
plished using synthetic electrochem- few of the many specific examples that depending upon whether a divided cell,
istry in the future. exist are portrayed in Fig. 3. Notice that or a single cell at high current density, is
even aryl groups,2 esters,3 and nitriles4 utilized (Fig. 3, example (h)). Given the
Cathodic Reductions can participate (Reactions (a), (b), and functional group equivalence of a nitro
(f)); that four membered rings can be group to a carbonyl adds interest to
It can be argued that the carbonyl is constructed (Reaction (d));5 and that these transformations.
the most versatile and important func- hindered quaternary centers can be It is difficult to imagine a method
tional group in organic chemistry. Its assembled in high yield (Reaction (e)).6 better suited to the recycling of reagents
polarization renders the carbonyl car- Thus, the chemistry provides a conve- than is electrochemistry. A recent review
bon susceptible to nucleophilic attack. nient means to synthesize a variety of entitled “Environmental Protection and
As indicated in the introduction, reduc- building blocks, some of which have Economization of Resources by Elec-
tion reverses the polarity so that the proven useful in the total synthesis of troorganic and Electroenzymatic Synthe-
carbonyl carbon becomes nucleophilic. natural products (Reactions (e) and (f)).7 ses” elaborates upon this notion.12 The
Electron deficient alkenes display simi- We do not mean to imply that only authors highlight the electrochemical
lar characteristics. Both the carbonyl carbonyl containing substrates are use- generation of redox reagents (mediators)
carbon and that positioned β to an α, β- ful. This is by no means the case. Many and their regeneration at the electrode
unsaturated carbonyl compound, for other functional groups can, and do par- for reuse, the utility of paired electrosyn-
example, display electrophilic charac- ticipate in reductive coupling reactions.8 thesis and the design and utility of elec-
ter. Once reduced, both sites assume Imines, for example, undergo electrohy- troenzymatic syntheses.
nucleophilic characteristics. drocyclization.9 A particularly interest- While many researchers have used
Figure 2 illustrates a number of bond ing example from Shono’s group illus- mediators in creative and useful ways,
constructions and functional group trates the utility of the process as a route we site but two examples, both from
arrays that are accessible using the car- to C2 symmetric diamine ligands that Utley’s laboratory. The first example is
bonyl (left) or the electron deficient have been used to activate normally particularly intriguing in that the medi-
alkene (right) radical anion building unreactive dialkyl zinc reagents toward ator, maleic anhydride, also serves as the
Anodic Oxidations
Trapping Reactions