Photoinduced Regiodivergent and Enantioselective Cross-Coupling of Glycine Derivatives with Hydrocarbon Feedstocks

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 2, 2025

Regiodivergent asymmetric synthesis represents a transformative strategy for the efficient generation of structurally diverse chiral products from single set starting materials, significantly enriching their enantiomeric composition. However, design radical-mediated regiodivergent and enantioselective reactions that can accommodate wide range functional groups substrates has posed significant challenges. The obstacles primarily lie in switching regioselectivity achieving high enantiodiscrimination, especially when dealing with high-energy intermediates. To address these issues, we have developed new catalytic system integrates photoinduced hydrogen atom transfer (HAT) copper catalysis, involving fine-tuning ligands, additives, other reaction parameters. facilitates cross-couplings between N-aryl glycine ester/amide derivatives abundant hydrocarbon feedstocks through strong C(sp3)–H bond activation. This approach allows controlled stereoselective formation C(sp3)–C(sp3) C(sp3)–N bonds, yielding rich variety C- or N-alkylated esters amides commendable yields (up to 92% yield), exclusive regioselectivities (typically >20:1 rr), enantioselectivities 96% ee). Our methodology not only provides promising avenue incorporation alkyl functionalities onto specific sites biologically molecules but also offers practical while simultaneously induction within photochemical reactions.

Язык: Английский

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Desymmetrization–Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 18892 - 18898

Опубликована: Июль 5, 2024

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated synthesis series chiral functionalized cyclopropanes with high yield, enantioselectivity, diastereoselectivity (44 examples, up 93% yield >99% ee). A possible mechanism involving cyclopropene desymmetrization Co-H species imine addition Co-alkyl was proposed. study provides novel route important extends frontier metallaphotoredox

Язык: Английский

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A General Copper‐Box System for the Asymmetric Arylative Functionalization of Benzylic, Propargylic or Allenylic Radicals

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июль 27, 2024

Abstract Radical‐involved arylative cross‐coupling reactions have recently emerged as an attractive strategy to access valuable aryl‐substituted motifs. However, there still exist several challenges such limited scope of radical precursors/acceptors, and lack general asymmetric catalytic systems, especially regarding the multicomponent variants. Herein, we reported a copper‐Box system for three‐component vinylarenes 1,3‐enynes, with oxime carbonates aryl boronic acids. The proceed under practical conditions in absence or presence visible‐light irradiation, affording chiral 1,1‐diarylalkanes, benzylic alkynes allenes good enantioselectivities. Mechanistic studies imply that copper/Box complexes play dual role both generation ensuing cross‐coupling. In cases irradiation could improve activity complex toward initial generation, enabling better efficiency match between formation

Язык: Английский

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Unusual Regioselective C–H Difluoroalkylation of Heteroarenes under Photoredox Catalysis

Organic Letters, Год журнала: 2024, Номер 26(24), С. 5098 - 5104

Опубликована: Июнь 7, 2024

We disclose a new general strategy for the site-selective difluoroalkylation of nonprefunctionalized heteroarenes, such as quinoxaline at C-8 position, and benzothiadiazole, benzoxadiazole, benzothiazole C-4 position via consecutive organophotoredox-catalyzed radical–radical cross-coupling base-assisted hydrogen abstraction reactions. The current methodology represents direct difluoroalkylative to allow broad functional group tolerance wide substrate scope in good excellent yields. Careful experimental investigations detailed DFT calculations revealed exact site-selectivity heteroarenes possible mechanistic pathway.

Язык: Английский

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Copper-Catalyzed sp² C–H Arylation and Alkynylation of Allenes via Hydrogen Atom Abstraction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(35), С. 24689 - 24698

Опубликована: Авг. 21, 2024

Development of methods for the sp2 C–H transformations allenes has received much attention, and it presents a powerful tool synthesis complicated allene-containing bioactive molecules. With copper-catalyzed radical relay, allenic arylation alkynylation were established herein, using various aryl boronic acids trimethoxysilyl-substituted alkynes as carbon nucleophiles electrophilic N–F reagents nitrogen-centered precursors. These featured excellent site selectivity to deliver fully substituted efficiently. Moreover, with silyl-substituted substrates, subsequent dual functionalization process was well, which allowed divergent multifunctionalized allenes, significantly expanding their chemical spaces.

Язык: Английский

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Hydrogen Bonding-Induced Aggregation of Chiral Functionalized AuNS@Ag NPs for Photothermal Enantioanalysis

Analytical Chemistry, Год журнала: 2024, Номер 96(16), С. 6292 - 6300

Опубликована: Апрель 10, 2024

Toward the challenges of signaling transduction amplified in enantioselective recognition, we herein devised an innovative strategy for highly selective recognition amino acids and their derivatives, leveraging photothermal effects. In this approach, bifunctional l-ascorbic acid is employed to reduce silver ions

Язык: Английский

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A General Copper-Box System for the Asymmetric Ary-lative Functionalization of Benzylic, Propargylic or Allenylic Radicals

Опубликована: Июнь 12, 2024

Radical-involved arylative cross-coupling reactions have recently emerged as an attractive strategy to access valuable aryl-substituted motifs. However, there still exist several challenges such limited scope of radi-cal precursors/acceptors, and lack general asymmetric catalytic systems, especially regarding the multicom-ponent variants. Herein, we reported a copper-Box system for three-component vinylarenes 1,3-enynes, with oxime carbonates aryl boronic acids. The proceed under practical conditions in absence or presence visible-light irradiation, affording chiral 1,1-diarylalkanes, benzylic alkynes allenes good enantioselectivities. Mechanistic studies imply that copper/Box complexes play dual role both radical generation ensuing cross-coupling. In cases irradiation could improve activity complex toward initial generation, enabling better efficiency match between formation

Язык: Английский

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Construction of planar chiral [2,2]paracyclophanes via photoinduced cobalt-catalyzed desymmetric addition

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

Опубликована: Апрель 29, 2025

Язык: Английский

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Unlocking Epoxide Radical Anion Reactivity for Asymmetric Cross-Coupling by Copper Metallaphotoredox

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 22, 2025

The ability to tame radical anions that feature both an unpaired spin and a charge is critical for synthetic chemistry, enabling the construction of diverse chemical bonds via unique reaction pathways promoting advances in area synthesis. In this regard, C(sp3)-rich epoxide are particularly attractive but often elusive, highly reactive intermediates. Classic methods access exploit single-electron chemistry by using dissolving alkali, sacrificial electrodes, or redox metals. However, these prohibitive because reagent safety issues over-reduction, limiting their wide implementation, especially asymmetric Herein, we realize copper metallaphotoredox platform unlock anion reactivity, allowing controlled generation enantioconvergent cross-coupling with diverse, readily available partners distonic These discoveries permit regio-, chemo-, enantioselective hydrocyanation hydroalkynylation, thereby providing general solution challenge anion-mediated diversification.

Язык: Английский

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Catalyst-free synthesis of hydrazino-containing glycine derivatives via a diaziridine in-situ formation/ring-opening cascade

Green Chemistry, Год журнала: 2024, Номер 26(16), С. 9104 - 9109

Опубликована: Янв. 1, 2024

A green and efficient method for the synthesis of glycine derivatives from amines, azodicarboxylates, diazoalkanes has been developed. This multicomponent reaction occurred under mild conditions in absence any catalysts or additives.

Язык: Английский

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