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Radical Oxidation of Allylic and Benzylic Alcohols01:21

Radical Oxidation of Allylic and Benzylic Alcohols

Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride01:26

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation01:22

Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation

Baeyer–Villiger oxidation converts aldehydes to carboxylic acids and ketones to esters. The reaction uses peroxy acids or peracids and is often catalyzed by acid. The reaction is named after its pioneers, Adolf von Baeyer and Victor Villiger. The reaction is achieved by a wide range of peracids such as m-chloroperoxybenzoic acid (mCPBA), perbenzoic acid (C6H5COOOH), peracetic acid (CH3COOOH), hydrogen peroxide (H2O2), and tert-butyl hydroperoxide (t-BuOOH).
The carbonyl center is activated by...
Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism01:18

Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism

Birch reduction uses solvated electrons as reducing agents. The reaction converts benzene to 1,4-cyclohexadiene. The reaction proceeds by the transfer of a single electron to the ring to form a benzene radical anion. This anion is highly basic—it abstracts a proton from the alcohol to form a cyclohexadienyl radical. Another single electron transfer gives the cyclohexadienyl anion. A proton transfer from the alcohol forms 1,4-cyclohexadiene. Since this reduction occurs via radical anion...
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For instance, consider...
Reactions at the Benzylic Position: Halogenation01:11

Reactions at the Benzylic Position: Halogenation

Benzylic halogenation takes place under conditions that favor radical reactions such as heat, light, or a free radical initiator like peroxide.

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Updated: Jul 14, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Published on: April 22, 2016

Repurposing Thiamine-Dependent Benzaldehyde Lyases as Visible-Light-Driven Radical Acyltransferases.

Yuanyuan Xu1,2, Xichao Peng1, Xiaoqiang Huang1

  • 1State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), Frontier Interdisciplinary Science Research Center, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.

Accounts of Chemical Research
|July 13, 2026
PubMed
Summary

Researchers developed a synergistic photoredox/thiamine radical biocatalysis to achieve asymmetric radical acylations. This novel approach repurposes thiamine diphosphate (ThDP)-dependent enzymes for challenging radical transformations with high stereochemical control.

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Light-driven Enzymatic Decarboxylation
09:58

Light-driven Enzymatic Decarboxylation

Published on: May 22, 2016

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Last Updated: Jul 14, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
06:49

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Published on: April 22, 2016

Light-driven Enzymatic Decarboxylation
09:58

Light-driven Enzymatic Decarboxylation

Published on: May 22, 2016

Area of Science:

  • Biocatalysis and Organic Synthesis
  • Enzyme Engineering and Mechanistic Enzymology

Background:

  • Thiamine diphosphate (ThDP)-dependent enzymes are crucial for C-C bond formation via umpolung mechanisms.
  • Existing biomimetic N-heterocyclic carbene (NHC) catalysts struggle with enantioselective cross-coupling of prochiral radicals due to intermediate reactivity and chiral environment limitations.
  • Previous ThDP enzyme pathways were primarily two-electron processes, with only a few known radical pathways (e.g., PFOR) not yet applied to asymmetric radical reactions.

Purpose of the Study:

  • To develop a synergistic photoredox/thiamine radical biocatalysis for asymmetric radical acylations.
  • To overcome the challenge of stereochemical control in enantioselective cross-coupling involving prochiral C-centered radicals.
  • To repurpose ThDP-dependent enzymes, specifically benzaldehyde lyase (PfBAL), into versatile radical acyltransferases (RATs).

Main Methods:

  • Integration of visible-light photoredox catalysis with a thiamine-dependent enzyme (Pseudomonas fluorescens PfBAL).
  • Activation of aldehyde substrates by PfBAL to form enzymatic Breslow intermediates.
  • Concurrent generation of prochiral C-centered radicals and enzyme-bound thiamine-derived ketyl radicals via photoredox catalysis.
  • Protein engineering of PfBAL to create a precise chiral environment for enantioselective radical cross-coupling.

Main Results:

  • Successful demonstration of synergistic photoredox/thiamine radical catalysis for decarboxylative radical acylation using N-(acyloxy)phthalimides and benzaldehyde.
  • Extension of the methodology to diverse challenging transformations, including C(sp3)-H acylation, acylation via nitrogen-centered radicals, and three-component couplings.
  • Construction of all-carbon quaternary stereocenters with minimally differentiated alkyl substituents.
  • Identification of key residues (480 and 481) in PfBAL through protein engineering and computational studies responsible for high enantioselectivity.

Conclusions:

  • Repurposed ThDP-dependent PfBAL into a versatile radical acyltransferase (RAT), expanding enzymatic reactivity.
  • Established a generalizable platform for controlling fleeting radical intermediates using a combination of chemomimetic and biomimetic strategies.
  • Demonstrated the potential for future advancements using AI-assisted protein design for broader applications of thiamine-dependent enzymes.