Search research articles

ABOUT JoVE

Overview Leadership Blog JoVE Help Center

AUTHORS

Publishing Process Editorial Board Scope & Policies Peer Review FAQ Submit

LIBRARIANS

Testimonials Subscriptions Access Resources Library Advisory Board FAQ

RESEARCH

JoVE Journal Methods Collections JoVE Encyclopedia of Experiments Archive

EDUCATION

JoVE Core JoVE Business JoVE Science Education JoVE Lab Manual Faculty Resource Center Faculty Site

Terms & Conditions of Use

Related Concept Videos

Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration

Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration

The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.

Hydroboration-Oxidation of Alkenes

Hydroboration-Oxidation of Alkenes

In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.

Preparation of Alcohols via Addition Reactions

Preparation of Alcohols via Addition Reactions

Overview
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...

Regioselectivity and Stereochemistry of Hydroboration

Regioselectivity and Stereochemistry of Hydroboration

A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...

Regioselectivity of Electrophilic Additions-Peroxide Effect

Regioselectivity of Electrophilic Additions-Peroxide Effect

In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.

Thermal and Photochemical Electrocyclic Reactions: Overview

Thermal and Photochemical Electrocyclic Reactions: Overview

Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by

Same author

Localized sample-based quantum diagonalization for strongly correlated chemistry.

Proceedings of the National Academy of Sciences of the United States of America·2026

Same author

Ultrafast excited-state proton transfer dynamics using linearized pair-density functional theory.

Chemical science·2026

Same author

C(sp<sup>3</sup>)-F Adsorption Implicated for Reductive Activation at Ag Electrodes.

ACS electrochemistry·2026

Same author

From Oxo to Oxyl to Biradical: Systematic Multireference Calculations of Methane Activation at MOF Nodes.

Journal of the American Chemical Society·2026

Same author

Mg<sup>2+</sup> Catalyzes Nonenzymatic RNA Primer Extension through a Concerted Outer-Sphere Mechanism.

Journal of the American Chemical Society·2026

Same author

Profile of Richard Robson, Susumu Kitagawa, and Omar M. Yaghi: 2025 Nobel laureates in Chemistry.

Proceedings of the National Academy of Sciences of the United States of America·2026

Search research articles

Related Experiment Video

Updated: Jun 20, 2025

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

Published on: August 23, 2018

Competitive Valerate Binding Enables RuO₂-Mediated Butene Electrosynthesis in Water.

Špela Kunstelj¹, Andrea Darù¹, Arturo Sauza-de la Vega¹

¹Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.

Journal of the American Chemical Society

|July 17, 2024

Summary

Sustainable butene production via valeric acid oxidation is achieved through ruthenium dioxide (RuO2) anodes. Carboxylate binding to the RuO2 surface suppresses oxygen evolution, enabling selective outer-sphere electron transfer for decarboxylation.

More Related Videos

Efficient Synthesis of Polyfunctionalized Benzenes in Water via Persulfate-promoted Benzannulation of α,β-Unsaturated Compounds and Alkynes

Efficient Synthesis of Polyfunctionalized Benzenes in Water via Persulfate-promoted Benzannulation of α,β-Unsaturated Compounds and Alkynes

Published on: December 16, 2019

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Published on: June 21, 2017

Related Experiment Videos

Last Updated: Jun 20, 2025

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

Published on: August 23, 2018

Efficient Synthesis of Polyfunctionalized Benzenes in Water via Persulfate-promoted Benzannulation of α,β-Unsaturated Compounds and Alkynes

Efficient Synthesis of Polyfunctionalized Benzenes in Water via Persulfate-promoted Benzannulation of α,β-Unsaturated Compounds and Alkynes

Published on: December 16, 2019

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Published on: June 21, 2017

Area of Science:

Electrochemistry
Sustainable Chemistry
Surface Science

Background:

Valeric acid, derived from cellulose, offers a sustainable feedstock for producing valuable chemicals like butene via oxidation.
The mechanism of oxidative decarboxylation at electrode surfaces, specifically the role of inner-sphere versus outer-sphere electron transfer, remains unclear.
Ruthenium dioxide (RuO2) is a promising anode material for electrochemical transformations.

Purpose of the Study:

To elucidate the mechanism of RuO2-mediated oxidative decarboxylation of valeric acid to butene.
To investigate the role of the electrode surface in mediating electron transfer and product selectivity.
To understand how the surface chemistry of RuO2 influences the competition between decarboxylation and oxygen evolution reactions.

Main Methods:

Electrochemical measurements to study reaction kinetics and potentials.
In situ spectroscopy to probe surface species and reaction intermediates.
Computational studies to model electron transfer mechanisms.
Reactivity studies to assess product formation and selectivity.

Main Results:

Carboxylate species derived from valeric acid bind to RuO2 anode surfaces at potentials relevant for butene formation.
Bound carboxylates effectively impede the competing oxygen evolution reaction (OER).
An outer-sphere electron transfer mechanism is implicated for the decarboxylation process, distinct from OER.

Conclusions:

The surface chemistry of RuO2 electrodes plays a critical role in achieving high selectivity for non-Kolbe oxidative decarboxylation.
Binding of carboxylate intermediates to the RuO2 surface suppresses parasitic OER, favoring butene production.
These findings provide interfacial design principles for developing selective electrochemical systems utilizing water as an oxidant for sustainable chemical synthesis.