The Merger of Aryl Radical-Mediated Halogen-Atom Transfer (XAT) and Copper Catalysis for the Modular Cross-Coupling-Type Functionalization of Alkyl Iodides

ACS Catalysis, Год журнала: 2023, Номер 13(7), С. 4985 - 4991

Опубликована: Март 28, 2023

Here, we report a toolbox strategy to cross-couple unactivated secondary alkyl iodides with various N-, O-, and C-based nucleophiles. This harnesses the ability of photoredox-generated phenyl radicals mediate halogen-atom transfer (XAT) convert into corresponding radicals. These species engage in second catalytic cycle, mediated by copper, which enables C–N/O/C bond formation

Язык: Английский

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Nickel-electrocatalysed C(sp3)–C(sp3) cross-coupling of unactivated alkyl halides

Nature Catalysis, Год журнала: 2024, Номер 7(4), С. 412 - 421

Опубликована: Фев. 23, 2024

Язык: Английский

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Boryl radical-mediated halogen-atom transfer enables arylation of alkyl halides with electrophilic and nucleophilic coupling partners

Nature Synthesis, Год журнала: 2024, Номер 3(10), С. 1221 - 1230

Опубликована: Июль 1, 2024

Язык: Английский

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The Merger of Benzophenone HAT Photocatalysis and Silyl Radical-Induced XAT Enables Both Nickel-Catalyzed Cross-Electrophile Coupling and 1,2-Dicarbofunctionalization of Olefins

ACS Catalysis, Год журнала: 2022, Номер 12(18), С. 11216 - 11225

Опубликована: Сен. 1, 2022

A strategy for both cross-electrophile coupling and 1,2-dicarbofunctionalization of olefins has been developed. Carbon-centered radicals are generated from alkyl bromides by merging benzophenone hydrogen atom transfer (HAT) photocatalysis silyl radical-induced halogen (XAT) subsequently intercepted a nickel catalyst to forge the targeted C(sp3)-C(sp2) C(sp3)-C(sp3) bonds. The mild protocol is fast scalable using flow technology, displays broad functional group tolerance, amenable wide variety medicinally relevant moieties. Mechanistic investigations reveal that ketone catalyst, upon photoexcitation, responsible direct activation silicon-based XAT reagent (HAT-mediated XAT) furnishes radical ultimately involved in turnover catalytic cycle.

Язык: Английский

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Aryl Radical Enabled, Copper-Catalyzed Sonogashira-Type Cross-Coupling of Alkynes with Alkyl Iodides

ACS Catalysis, Год журнала: 2023, Номер 13(4), С. 2761 - 2770

Опубликована: Фев. 8, 2023

Despite the success of Sonogashira coupling for synthesis arylalkynes and conjugated enynes, engagement unactivated alkyl halides in such reactions remains historically challenging. We report herein a strategy that merges Cu-catalyzed alkyne transfer with aryl radical activation carbon-halide bonds to enable general approach iodides terminal alkynes. This unprecedented Sonogashira-type cross-coupling reaction tolerates broad range functional groups has been applied late-stage densely functionalized pharmaceutical agents as well positron emission tomography tracers.

Язык: Английский

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Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(20), С. 10930 - 10937

Опубликована: Май 15, 2023

Amines and carboxylic acids are abundant synthetic building blocks that classically united to form an amide bond. To access new pockets of chemical space, we interested in the development amine-acid coupling reactions complement coupling. In particular, formation carbon-carbon bonds by formal deamination decarboxylation would be impactful addition synthesis toolbox. Here, report a cross-coupling alkyl amines aryl C(sp

Язык: Английский

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An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer

ChemCatChem, Год журнала: 2023, Номер 15(21)

Опубликована: Авг. 14, 2023

Abstract The merging of photocatalysis with halogen‐atom transfer (XAT) processes has proven to be a versatile tool for the generation carbon‐centered radicals in organic synthesis. XAT are unique that they generate without requiring use strong reductants necessary traditional single electron (SET) activation halides. Pathways achieve synthetic applications can categorized into three major sections: i) heteroatom‐based activators, ii) metal‐based and iii) carbon‐based activators among which α‐aminoalkyl have taken center stage. Access these as reagents gained significant attention past few years due robustness reactions, simplicity required, broadness their applications. Generation is simply achieved through oxidation tertiary amines, after deprotonation at α‐position generates radicals. Due wide scope amines available tunable nucleophilicity radical formed, this strategy become an attractive alternative heteroatom/metal‐based XAT. In minireview, we focus our on recent (2020–2023) developments uses robust technology mediate processes.

Язык: Английский

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Catalytically Relevant Organocopper(III) Complexes Formed through Aryl-Radical-Enabled Oxidative Addition

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(22), С. 15176 - 15185

Опубликована: Май 21, 2024

Stepwise oxidative addition of copper(I) complexes to form copper(III) species via single electron transfer (SET) events has been widely proposed in copper catalysis. However, direct observation and detailed investigation these fundamental steps remain elusive owing largely the typically slow rate instability species. We report herein a novel aryl-radical-enabled stepwise pathway that allows for formation well-defined alkyl–CuIII from CuI complexes. The process is enabled by SET an aryl diazonium salt CuII radical. Subsequent iodine abstraction alkyl iodide radical affords radical, which then reacts with complex. structure resultant [(bpy)CuIII(CF3)2(alkyl)] characterized NMR spectroscopy X-ray crystallography. Competition experiments have revealed at different iodides undergo consistent carbon-centered radicals. intermediate formed during identified as four-coordinate complex, [CuII(CH3CN)2(CF3)2], through electronic paramagnetic resonance (EPR) studies. catalytic relevance high-valent organo-CuIII demonstrated C–C bond-forming reductive elimination reactivity. Finally, localized orbital bonding analysis formal CuIII indicates inverted ligand fields σ(Cu–CH2) bonds. These results demonstrate catalysis provide general strategy investigate

Язык: Английский

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Iodoarene-directed photoredox β-C(sp³)–H arylation of 1-(o-iodoaryl)alkan-1-ones with cyanoarenes via halogen atom transfer and hydrogen atom transfer

Chemical Science, Год журнала: 2024, Номер 15(17), С. 6522 - 6529

Опубликована: Янв. 1, 2024

Site selective functionalization of inert remote C(sp

Язык: Английский

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Enantioselective reductive cross-couplings to forge C(sp2)–C(sp3) bonds by merging electrochemistry with nickel catalysis

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 28, 2025

Abstract Motivated by the inherent benefits of synergistically combining electrochemical methodologies with nickel catalysis, we present here a Ni-catalyzed enantioselective electroreductive cross-coupling benzyl chlorides aryl halides, yielding chiral 1,1-diaryl compounds good to excellent enantioselectivity. This catalytic reaction can not only be applied chlorides/bromides, which are challenging access other means, but also containing silicon groups. Additionally, absence sacrificial anode lays foundation for scalability. The combination cyclic voltammetry analysis electrode potential studies suggests that Ni I species activate halides via oxidative addition and alkyl single electron transfer.

Язык: Английский

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