Electro-inductive effect: Electrodes as functional groups with tunable electronic properties

In organic chemistry, reaction rates are often sensitive to substituents that either donate or withdraw electron density from a reactive carbon center. Heo et al. now report that when reactants are tethered to an electrode, the polarization effect of an applied potential can exert an analogous influ...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2020-10, Vol.370 (6513), p.214-219
Main Authors: Heo, Joon, Ahn, Hojin, Won, Joonghee, Son, Jin Gyeong, Shon, Hyun Kyong, Lee, Tae Geol, Han, Sang Woo, Baik, Mu-Hyun
Format: Article
Language:English
Subjects:
Carbodiimide
Carboxylic acids
Chemical reactions
Coupling (molecular)
Cross coupling
Electric potential
Electrode polarization
Electrodes
Electron density
Esters
Functional groups
Gold
Open circuit voltage
Organic chemistry
Polarization
Reagents
Substrates
Voltage
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Summary:In organic chemistry, reaction rates are often sensitive to substituents that either donate or withdraw electron density from a reactive carbon center. Heo et al. now report that when reactants are tethered to an electrode, the polarization effect of an applied potential can exert an analogous influence, essentially acting as a tunable functional group. The authors demonstrate rate modulations in ester hydrolysis and arene cross-coupling, as well as a two-step acid-to-amide conversion that benefits from inversion of the polarization midway through the reaction. Science , this issue p. 214 Polarizing organic molecules bound to an electrode surface can tune their reactivity. In place of functional groups that impose different inductive effects, we immobilize molecules carrying thiol groups on a gold electrode. By applying different voltages, the properties of the immobilized molecules can be tuned. The base-catalyzed saponification of benzoic esters is fully inhibited by applying a mildly negative voltage of –0.25 volt versus open circuit potential. Furthermore, the rate of a Suzuki-Miyaura cross-coupling reaction can be changed by applying a voltage when the arylhalide substrate is immobilized on a gold electrode. Finally, a two-step carboxylic acid amidation is shown to benefit from a switch in applied voltage between addition of a carbodiimide coupling reagent and introduction of the amine.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.abb6375