Related Experiment Video
Updated: Dec 10, 2025
![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)
07:12
Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
6.5K
In Situ Reduction and Functionalization of Polycyclic Quinones
Karl J Thorley1,2, Yang Song3, Sean R Parkin1
1Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506, United States.
Organic Letters
|September 3, 2020
Summary
Researchers unexpectedly formed acenes when attempting to functionalize polycyclic quinones using lithium diisopropylamide. This novel electron transfer reaction opens new pathways for synthesizing complex organic molecules.
Area of Science:
- Organic Chemistry
- Synthetic Methodology
Background:
- Polycyclic quinones are important structural motifs in various chemical applications.
- Direct functionalization of quinones can be challenging due to their reactivity.
- Lithium diisopropylamide is a common strong base in organic synthesis.
Purpose of the Study:
- To explore the reactivity of polycyclic quinones with lithium diisopropylamide.
- To develop a new synthetic route for acene formation.
- To investigate the functionalization of quinone radical anions.
Main Methods:
- Reaction of polycyclic quinones with lithium diisopropylamide.
- Electron transfer mechanism investigation.
- Synthesis and isolation of siloxy derivatives.
Main Results:
- Unexpected formation of acenes via electron transfer from lithium diisopropylamide to quinones.
- Radical anion intermediates react with electrophiles.
- Synthesized siloxy derivatives were isolable but photolabile.
- In situ generation of reduced intermediates enabled hydroquinone functionalization.
Conclusions:
- Lithium diisopropylamide mediates a novel electron transfer pathway for quinone functionalization, leading to acene synthesis.
- The developed method offers a convenient approach for handling oxidatively sensitive hydroquinones.
- Further research is needed to improve the photostability of synthesized derivatives.
More Related Videos
Related Concept Videos
01:17Oxidation of Phenols to Quinones
4.2K
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...
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...
4.2K
01:10Radical Chain-Growth Polymerization: Overview
3.0K
Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
3.0K
01:27Phase I Reactions: Reductive Reactions
435
Phase I biotransformation reductive reactions are chemical processes that modify drugs by introducing or revealing polar functional groups via reduction. Enzymes called reductases catalyze these reactions, playing a pivotal role in drug metabolism by transforming lipophilic drugs into more polar, water-soluble metabolites for easy excretion. An essential type of reductive reaction is the carbonyl group reduction, where aldehydes and ketones are reduced to alcohols. An example is the...
435
01:29Preparation of Amines: Reduction of Oximes and Nitro Compounds
4.5K
Oximes can be reduced to primary amines using catalytic hydrogenation, hydride reduction, or sodium metal reduction. The reduction of aliphatic and aromatic nitro compounds to primary amines takes place by either catalytic hydrogenation or by using active metals like Fe, Zn, and Sn in the presence of an acid.
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
4.5K
01:18Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism
2.5K
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...
2.5K
01:17Pericyclic Reactions: Introduction
9.5K
Pericyclic reactions are organic reactions that occur via a concerted mechanism without generating any intermediates. The reactions proceed through the movement of electrons in a closed loop to form a cyclic transition state, where rearrangement of the σ and π bonds yields specific products.
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic...
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic...
9.5K