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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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A Selective C-C Bond Cleavage Strategy Promoted by Visible Light
Rafael D C Gallo1, Marcelo Duarte1, Amanda F da Silva1
1State University of Campinas, Institute of Chemistry, Rua Monteiro Lobato 270, 13083-862 Campinas, São Paulo, Brazil.
Organic Letters
|November 3, 2021
Summary
This study introduces a new visible-light reaction for creating 1,4-dicarbonyl compounds from aryldiazoacetates and 1,3-diketones. The metal-free method offers practical C-C bond insertions with good yields and selectivity.
Area of Science:
- Organic Chemistry
- Photochemistry
- Synthetic Methodology
Background:
- Visible-light photocatalysis has emerged as a powerful tool in organic synthesis.
- Developing efficient and practical methods for C-C bond formation is crucial in synthetic chemistry.
- 1,3-Diketones are versatile building blocks in organic synthesis.
Purpose of the Study:
- To develop a novel visible-light-promoted reaction for the synthesis of 1,4-dicarbonyl compounds.
- To explore the reaction between aryldiazoacetates and 1,3-diketones for C-C bond insertion.
- To establish a practical, metal-free synthetic route.
Main Methods:
- Visible-light irradiation of aryldiazoacetates and 1,3-diketones.
- Optimization of reaction conditions including solvent, light source, and concentration.
- Mechanistic studies involving intermediate trapping and spectroscopic analysis.
Main Results:
- Successful C-C bond insertion between aryldiazoacetates and 1,3-diketones.
- Formation of 1,4-dicarbonyl compounds in good yields and selectivities.
- Demonstration of air and moisture tolerance, and metal-free conditions.
Conclusions:
- A new, practical, and efficient visible-light-promoted reaction for synthesizing 1,4-dicarbonyl compounds has been developed.
- The reaction proceeds via a key cyclopropanol intermediate, highlighting a novel mechanistic pathway.
- This metal-free transformation offers a valuable addition to the synthetic chemist's toolkit for constructing complex molecules.
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