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Oxidation and Reduction of Organic Molecules01:19

Oxidation and Reduction of Organic Molecules

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Energy production within a cell involves many coordinated chemical pathways. Most of these pathways are combinations of oxidation and reduction reactions, which occur at the same time. An oxidation reaction strips an electron from an atom in a compound, and the addition of this electron to another compound is a reduction reaction. Because oxidation and reduction usually occur together, these pairs of reactions are called redox reactions.
The removal of an electron from a molecule, results in a...
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Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids02:04

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

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Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
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Acid-Catalyzed Ring-Opening of Epoxides02:24

Acid-Catalyzed Ring-Opening of Epoxides

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Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
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Oxidation of Phenols to Quinones01:17

Oxidation of Phenols to Quinones

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In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...
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Autoxidation of Ethers to Peroxides and Hydroperoxides02:23

Autoxidation of Ethers to Peroxides and Hydroperoxides

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Ethers represent a class of chemical compounds that become more dangerous with prolonged storage because they tend to form explosive peroxides when standing in the air. Autoxidation is the spontaneous oxidation of a compound in air. In the presence of oxygen, ethers slowly oxidize to form hydroperoxides and dialkyl peroxides.
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Preparation of Epoxides03:00

Preparation of Epoxides

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Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of...
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Video Experimental Relacionado

Updated: Oct 8, 2025

Author Spotlight: Design and Evaluation of Au-Electroplated Carbon Fiber Cloth Electrodes for Hydrogen Peroxide Fuel Cells
06:39

Author Spotlight: Design and Evaluation of Au-Electroplated Carbon Fiber Cloth Electrodes for Hydrogen Peroxide Fuel Cells

Published on: October 20, 2023

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Electrorreducción por el epóxido

Cheng Huang1, Wan Ma1, Xuelian Zheng1

  • 1The Institute for Advanced Studies (IAS), Wuhan University, Wuhan 430072, P. R. China.

Journal of the American Chemical Society
|December 29, 2021
PubMed
Resumen
Este resumen es generado por máquina.

Este estudio introduce la hidrogenación electroquímica por epoxi­dos, un nuevo método para la síntesis de alcoholes. Se logra la apertura selectiva del anillo de Markovnikov o anti-Markovnikov sin metales de transición, ofreciendo una nueva y poderosa ruta sintética.

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Área de la Ciencia:

  • Química orgánica
  • La electroquímica
  • Catálisis

Sus antecedentes:

  • La hidrogenación selectiva de los epóxidos es una transformación clave para la síntesis de alcohol.
  • Los métodos existentes a menudo requieren catalizadores de metales de transición y luchan con la regioselectividad.
  • El desarrollo de una funcionalización de epóxido selectivo sin metales sigue siendo un desafío importante.

Objetivo del estudio:

  • Desarrollar un nuevo método electroquímico para la hidrogenación selectiva de los epóxidos.
  • Para lograr la síntesis directa de alcohol a partir de epoxidos utilizando electrones y protones como reductores.
  • Para explorar la regioselectividad de Markovnikov y anti-Markovnikov en la apertura del anillo epóxido.

Principales métodos:

  • Reducción electroquímica de los epóxidos utilizando electrones y protones.
  • Utilizando una amplia gama de epóxidos primarios, secundarios y terciarios.
  • Estudios mecanicistas que incluyen radicales intermedios in situ y análisis cinético.

Principales resultados:

  • Síntesis exitosa de diversos alcoholes primarios, secundarios y terciarios.
  • Demostración de la apertura selectiva del anillo de epóxido de Markovnikov y anti-Markovnikov.
  • Identificación de los factores que controlan la regioselectividad: estabilidad termodinámica de los radicales bencílicos (epoxidos de arilo) y control cinético (epoxidos de alquilo).

Conclusiones:

  • La hidrogenación electroquímica del epoxido proporciona una vía versátil y libre de metales para los alcoholes.
  • La regioselectividad puede controlarse con precisión en función del tipo de sustrato y los mecanismos de reacción.
  • Este enfoque ofrece una alternativa sostenible y eficiente para la síntesis de alcohol.