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1. Recent Advances in Dual Triplet Ketone/Transition-Metal Catalysis

   https://doi.org/10.1055/s-0042-1751444  

   Iziumchenko, Valeriia; Gevorgyan, Vladimir (July 2023, Synlett)

   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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2. Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

   https://doi.org/10.1002/anie.202115626  

   Schmidt‐Räntsch, Till; Verplancke, Hendrik; Lienert, Jonas N.; Demeshko, Serhiy; Otte, Matthias; Van Trieste, III, Gerard P.; Reid, Kaleb A.; Reibenspies, Joseph H.; Powers, David C.; Holthausen, Max C.; et al (January 2022, Angewandte Chemie International Edition)

   Abstract C−H amination and amidation by catalytic nitrene transfer are well‐established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C−H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd−N) with a diradical nitrogen ligand that is singly bonded to Pd^II. Despite the subvalent nitrene character, selective C−H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N₃SiMe₃. Based on these results, a photocatalytic protocol for aldehyde C−H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C−H nitrogen atom transfer offers facile access to primary amides after deprotection. 

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3. Silica‐PMMA hairy nanoparticles prepared via phase transfer‐assisted aqueous miniemulsion atom transfer radical polymerization

   https://doi.org/10.1002/pol.20200382  

   Wu, Dung‐Yi; Käfer, Florian; Diaco, Nicholas; Ober, Christopher K. (August 2020, Journal of Polymer Science)

   Abstract Hairy nanoparticles (HNPs) constitute a class of hybrid nanocomposites that are resistant to aggregation and agglomeration, although the green, large‐scale synthesis of HNPs remains a challenge. In this work, 25 nm‐diameter silica‐core HNPs with a poly(methyl methacrylate) (PMMA) shell were synthesized using a graft‐from approach in aqueous miniemulsion, employing atom transfer radical polymerization with activators regenerated by electron transfer (ARGET‐ATRP). In particular, this work used tetrabutylammonium bromide (TBAB)‐assisted phase transfer of monomer, markedly improving upon earlier methods by showing that phase transfer could take place in the absence of organic solvents. Furthermore, syntheses with selected monomer addition rates produced HNP graft densities ranging from 0.011 to 0.017 chains/nm²and shell thicknesses ranging from 2.5 to 11 nm. Finally, analysis of reaction kinetics revealed that shell growth reached completion in as little as 2 hr, confirmed by the synthesis of >1 g of PMMA‐shell HNPs in a reduced timeframe. 

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4. CdS Quantum Dot Gels as a Direct Hydrogen Atom Transfer Photocatalyst for C−H Activation

   https://doi.org/10.1002/anie.202403186  

   Liu, Daohua; Hazra, Atanu; Liu, Xiaolong; Maity, Rajendra; Tan, Ting; Luo, Long (August 2024, Angewandte Chemie International Edition)

   Abstract Here, we report CdS quantum dot (QD) gels, a three‐dimensional network of interconnected CdS QDs, as a new type of direct hydrogen atom transfer (d‐HAT) photocatalyst for C−H activation. We discovered that the photoexcited CdS QD gel could generate various neutral radicals, including α‐amido, heterocyclic, acyl, and benzylic radicals, from their corresponding stable molecular substrates, including amides, thio/ethers, aldehydes, and benzylic compounds. Its C−H activation ability imparts a broad substrate and reaction scope. The mechanistic study reveals that this reactivity is intrinsic to CdS materials, and the neutral radical generation did not proceed via the conventional sequential electron transfer and proton transfer pathway. Instead, the C−H bonds are activated by the photoexcited CdS QD gel via a d‐HAT mechanism. This d‐HAT mechanism is supported by the linear correlation between the logarithm of the C−H bond activation rate constant and the C−H bond dissociation energy (BDE) with a Brønsted slopeα=0.5. Our findings expand the currently limited direct hydrogen atom transfer photocatalysis toolbox and provide new possibilities for photocatalytic C−H activation. 

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5. Divergent Concerted Proton–Electron Transfer (CPET) and Hydrogen Atom Transfer (HAT) Pathways of Amidyl Radical Reactivity Enable Chemoselective Functionalization

   https://doi.org/10.1021/acs.orglett.5c03705  

   Handlin, Alexandra D; Leibfarth, Frank A; Alexanian, Erik J (October 2025, Organic Letters)

   Amidyl radicals mediate a diverse array of intermolecular aliphatic C(sp3)–H and decarboxylative functionalizations. Interestingly, we have observed that decarboxylative processes proceed with excellent chemoselectivity even with substrates containing weak C(sp3)–H bonds. Herein, we report a mechanistic basis for understanding this high chemoselectivity of amidyl radicals through divergent reaction pathways. A computational assessment of the transition state SOMOs and intrinsic bonding orbitals for amidyl radical hydrogen atom transfer (HAT) and concerted proton-electron transfer (CPET) processes support a shift in mechanism between aliphatic C(sp3)–H or carboxylic acid O–H abstraction, which is supported by experimental studies. These findings provide a rationale for the chemoselectivity of decarboxylative reactions mediated by amidyl radicals. 

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