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Abstract Dual light-excited ketone/transition-metal catalysis is a rapidly developing field of photochemistry. It allows for versatile functionalizations of C–H or C–X bonds enabled by triplet ketone acting as a hydrogen-atom-abstracting agent, a single-electron acceptor, or a photosensitizer. This review summarizes recent developments of synthetically useful transformations promoted by the synergy between triplet ketone and transition-metal catalysis. 1 Introduction 2 Triplet Ketone Catalysis via Hydrogen Atom Transfer 2.1 Triplet Ketones with Nickel Catalysis 2.2 Triplet Ketones with Copper Catalysis 2.3 Triplet Ketones with Other Transition-Metal Catalysis 3 Triplet Ketone Catalysis via Single-Electron Transfer 4 Triplet Ketone Catalysis via Energy Transfer 5 Conclusions
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Photooxidation of Polyolefins to Produce Materials with In‐Chain Ketones and Improved Materials Properties
Abstract Herein, we report a selective photooxidation of commodity postconsumer polyolefins to produce polymers with in‐chain ketones. The reaction does not involve the use of catalyst, metals, or expensive oxidants, and selectively introduces ketone functional groups. Under mild and operationally simple conditions, yields up to 1.23 mol % of in‐chain ketones were achieved. Installation of in‐chain ketones resulted in materials with improved adhesion of the materials and miscibility of mixed plastics relative to the unfunctionalized plastics. The introduction of ketone groups into the polymer backbone allows these materials to react with diamines, forming dynamic covalent polyolefin networks. This strategy allows for the upcycling of mixed plastic waste into reprocessable materials with enhanced performance properties compared to polyolefin blends. Mechanistic studies support the involvement of photoexcited nitroaromatics in consecutive hydrogen and oxygen atom transfer reactions.
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- Award ID(s):
- 2318141
- PAR ID:
- 10631296
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 64
- Issue:
- 5
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1002/anie.202418411
