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Updated: Jan 24, 2026
06:46
Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
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Intermolecular 2 + 2 Carbonyl-Olefin Photocycloadditions Enabled by Cu(I)-Norbornene MLCT
Daniel M Flores1, Valerie A Schmidt1
1Department of Chemistry and Biochemistry , University of California, San Diego , La Jolla , California 92093 , United States.
Journal of the American Chemical Society
|May 24, 2019
Summary
Researchers developed a novel copper(I) precatalyst for photocycloaddition reactions. This method enables the synthesis of oxetanes from alkyl ketones, overcoming limitations of traditional Paternò-Büchi reactions.
Area of Science:
- Organic Chemistry
- Photochemistry
- Catalysis
Background:
- The Paternò-Büchi reaction is a common method for synthesizing oxetanes via photocycloaddition.
- Traditional methods face limitations due to mechanistic constraints of carbonyl excitation and olefin interception, particularly with challenging substrates like alkyl ketones.
Purpose of the Study:
- To develop a new catalytic system for intermolecular 2 + 2 carbonyl-olefin photocycloaddition.
- To enable the use of alkyl ketones in oxetane formation, expanding the scope of this reaction.
Main Methods:
- Utilized a copper(I) precatalyst to selectively activate olefins through metal coordination.
- Investigated the reaction mechanism using mechanistic studies.
- Characterized the intermediate Cu-norbornene resting state.
Main Results:
- Achieved selective intermolecular 2 + 2 carbonyl-olefin photocycloaddition.
- Successfully employed challenging alkyl ketones as substrates.
- Identified a metal-ligand charge transfer (MLCT) process involving a Cu-norbornene intermediate leading to oxetane formation.
Conclusions:
- The developed Cu(I) precatalyst system effectively overcomes limitations of direct irradiation pathways for oxetane synthesis.
- This catalytic approach broadens the utility of photocycloaddition reactions for constructing oxetane motifs, especially from less reactive carbonyl compounds.
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