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Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

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.

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.

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.

Autoxidation of Ethers to Peroxides and Hydroperoxides

Autoxidation of Ethers to Peroxides and Hydroperoxides

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.

Oxidation of Phenols to Quinones

Oxidation of Phenols to Quinones

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 property is crucial in...

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 stereochemistry.

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Related Experiment Video

Updated: Jun 19, 2026

Light-driven Enzymatic Decarboxylation

Light-driven Enzymatic Decarboxylation

Published on: May 22, 2016

Hydroperoxylation by hydroxyethylphosphonate dioxygenase.

John T Whitteck¹, Robert M Cicchillo, Wilfred A van der Donk

¹Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Street, Urbana, Illinois 61801, USA.

Journal of the American Chemical Society

|October 21, 2009

Summary

Hydroxyethylphosphonate dioxygenase (HEPD) uses molecular oxygen to cleave 2-hydroxyethylphosphonate (2-HEP). The enzyme proceeds via hydroperoxylation followed by a Criegee rearrangement, not initial hydroxylation.

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Anaerobic Protein Purification and Kinetic Analysis via Oxygen Electrode for Studying DesB Dioxygenase Activity and Inhibition

Anaerobic Protein Purification and Kinetic Analysis via Oxygen Electrode for Studying DesB Dioxygenase Activity and Inhibition

Published on: October 3, 2018

Area of Science:

Biochemistry
Enzymology
Chemical Biology

Background:

Hydroxyethylphosphonate dioxygenase (HEPD) is an enzyme that catalyzes a unique O(2)-dependent carbon-carbon bond cleavage.
The reaction mechanism of HEPD has been debated, with two proposed pathways: initial hydroxylation or initial hydroperoxylation followed by a Criegee rearrangement.

Purpose of the Study:

To elucidate the precise mechanism of Hydroxyethylphosphonate dioxygenase (HEPD) in cleaving 2-hydroxyethylphosphonate (2-HEP).
To distinguish between proposed reaction pathways by synthesizing and testing substrate analogues.

Main Methods:

Synthesis of substrate analogues, including hydroxymethylphosphonate and 1-hydroxyethylphosphonate.
Enzymatic assays using synthesized analogues to observe reaction products.
Analysis of reaction products to determine the mechanistic pathway.

Main Results:

Hydroxymethylphosphonate was converted to phosphate and formate.
1-hydroxyethylphosphonate yielded acetylphosphate, an enzyme inhibitor.
(2R)-Hydroxypropylphosphonate showed partitioning, producing 2-oxopropylphosphonate and hydroxymethylphosphonate.

Conclusions:

Results strongly support a mechanism involving initial hydroperoxylation of the substrate.
The reaction proceeds via a Criegee rearrangement with a phosphorus-based migrating group.
The O-O bond of molecular oxygen remains intact until substrate activation.