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Related Concept Videos

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Radical Autoxidation01:20

Radical Autoxidation

The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form hydroperoxide. Autoxidation involves initiation, propagation, and termination steps. Many organic compounds are susceptible to autoxidation—especially ethers in the presence of oxygen, which form hydroperoxides. Even though this reaction is slow, old ether bottles contain small amounts of peroxide, which leads to laboratory explosions during ether...
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide02:44

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.
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids02:04

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.
Radical Anti-Markovnikov Addition to Alkenes: Mechanism01:17

Radical Anti-Markovnikov Addition to Alkenes: Mechanism

The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain reaction comprises initiation, propagation, and termination steps.
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy radical...
Radical Anti-Markovnikov Addition to Alkenes: Overview01:25

Radical Anti-Markovnikov Addition to Alkenes: Overview

The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.

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Updated: Jun 14, 2026

Monitoring the Reductive and Oxidative Half-Reactions of a Flavin-Dependent Monooxygenase using Stopped-Flow Spectrophotometry
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Monitoring the Reductive and Oxidative Half-Reactions of a Flavin-Dependent Monooxygenase using Stopped-Flow Spectrophotometry

Published on: March 18, 2012

Asymmetric Hydroamination Using Oxidative Radical Initiation in Flavin Enzymes.

Alexandra C Brown1, Carlos E Del Angel Aguilar1, Felix C Raps1

  • 1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.

Journal of the American Chemical Society
|June 12, 2026
PubMed
Summary
This summary is machine-generated.

Researchers engineered a flavin enzyme for asymmetric radical alkene hydroamination, creating chiral pyrrolidines with high selectivity. This breakthrough overcomes limitations in flavin photobiocatalysis by enhancing cofactor stability and enabling stereocontrolled radical reactions.

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Light-driven Enzymatic Decarboxylation
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Published on: May 22, 2016

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Last Updated: Jun 14, 2026

Monitoring the Reductive and Oxidative Half-Reactions of a Flavin-Dependent Monooxygenase using Stopped-Flow Spectrophotometry
12:08

Monitoring the Reductive and Oxidative Half-Reactions of a Flavin-Dependent Monooxygenase using Stopped-Flow Spectrophotometry

Published on: March 18, 2012

Simultaneous Measurement of Superoxide/Hydrogen Peroxide and NADH Production by Flavin-containing Mitochondrial Dehydrogenases
08:57

Simultaneous Measurement of Superoxide/Hydrogen Peroxide and NADH Production by Flavin-containing Mitochondrial Dehydrogenases

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Light-driven Enzymatic Decarboxylation
09:58

Light-driven Enzymatic Decarboxylation

Published on: May 22, 2016

Area of Science:

  • Biocatalysis
  • Organic Chemistry
  • Enzyme Engineering

Background:

  • Asymmetric radical alkene hydroamination is key for synthesizing chiral N-heterocycles.
  • Achieving stereoselectivity in these reactions remains a significant challenge.
  • Flavin photobiocatalysis is limited by the short excited-state lifetime of flavin quinones.

Purpose of the Study:

  • To engineer a flavin enzyme for efficient and stereoselective asymmetric radical alkene hydroamination.
  • To overcome the limitations of flavin photobiocatalysis related to cofactor excited-state lifetime.
  • To introduce novel mechanistic insights for broader photobiocatalysis applications.

Main Methods:

  • Rational mutagenesis of a flavin enzyme to tune photophysical properties and enhance excited-state lifetime.
  • Engineering the modified enzyme to catalyze asymmetric radical hydroaminations.
  • Investigating the role of exogenous cophotocatalysts as photoprotectants.
  • Analyzing the mechanism of enantiospecific termination of chiral radical intermediates.

Main Results:

  • An engineered flavin enzyme successfully catalyzed the formation of chiral pyrrolidines with high yield and enantioselectivity.
  • Mutagenesis yielded a flavin variant with a significantly prolonged excited-state lifetime.
  • The study demonstrated the utility of an exogenous cophotocatalyst in protecting the flavin cofactor.
  • Enantiospecific termination of radical intermediates was identified as a key stereocontrol mechanism.

Conclusions:

  • Engineered flavin enzymes can overcome limitations in photobiocatalysis for asymmetric synthesis.
  • This work provides a robust method for producing chiral pyrrolidines via radical hydroamination.
  • The mechanistic discoveries offer new strategies for advancing flavin-based photobiocatalysis and stereoselective transformations.