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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Transition-metal-catalyzed enantioselective C–N cross-coupling

Chemical Society Reviews, Год журнала: 2024, Номер 53(19), С. 9560 - 9581

Опубликована: Янв. 1, 2024

Chiral amine scaffolds are among the most important building blocks in natural products, drug molecules, and functional materials, which have prompted chemists to focus more on their synthesis. Among accomplishments chiral synthesis, transition-metal-catalyzed enantioselective C-N cross-coupling is considered one of efficient protocols. This approach combines traditional C(sp

Язык: Английский

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In situ copper photocatalysts triggering halide atom transfer of unactivated alkyl halides for general C(sp3)-N couplings

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 5, 2024

Abstract Direct reduction of unactivated alkyl halides for C(sp3)-N couplings under mild conditions presents a significant challenge in organic synthesis due to their low potential. Herein, we introduce an situ formed pyridyl-carbene-ligated copper (I) catalyst that is capable abstracting halide atom and generating radicals general visible light. Control experiments confirmed the mono-pyridyl-carbene-ligated complex active species responsible catalysis. Mechanistic investigations using transient absorption spectroscopy across multiple decades timescales revealed ultrafast intersystem crossing (260 ps) photoexcited complexes into long-lived triplet excited states (>2 μs). The non-Stern-Volmer quenching dynamics triplets by suggests association between halides, thereby facilitating abstraction atoms via inner-sphere single electron transfer (SET), rather than outer-sphere SET, formation subsequent cross couplings.

Язык: Английский

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A General Enantioselective α-Alkyl Amino Acid Derivatives Synthesis Enabled by Cobalt-Catalyzed Reductive Addition

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

Enantioenriched unnatural amino acids represent a prevalent motif in organic chemistry, with profound applications biochemistry, medicinal and materials science. Herein, we report cobalt-catalyzed aza-Barbier reaction of dehydroglycines unactivated alkyl halides to afford α-amino esters high enantioselectivity. This catalytic reductive alkylative addition protocol circumvents the use moisture-, air-sensitive organometallic reagents, stoichiometric chiral auxiliaries, enabling conversion variety primary, secondary, even tertiary α-alkyl-amino under mild conditions, thus leading broad functional group tolerance. The expedient access biologically active motifs demonstrates practicality this by reducing number synthetic steps enhancing efficiency.

Язык: Английский

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Copper-Catalyzed Asymmetric Nucleophilic Opening of 1,1,2,2-Tetrasubstituted Donor–Acceptor Cyclopropanes for the Synthesis of α-Tertiary Amines

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 26, 2024

Catalytic asymmetric transformation of donor–acceptor cyclopropanes (DACs) has been proven to be a highly valuable and robust strategy construct diverse types enantioenriched molecules. However, the use 1,1,2,2-tetrasubstituted DACs form products bearing quaternary stereocenters remains long-term unsolved challenge. Here, we report copper-catalyzed aminative ring opening tetrasubstituted alkynyl that delivers myriad α-tertiary amines with high levels enantioselectivities. The alkyne, amine, ester moieties within enable further applications, including synthesis bioactive Mechanistic studies indicate zwitterionic intermediate copper-acetylide unit plays key role in process, which represents new mode for achieving catalytic DACs.

Язык: Английский

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Research Progress in the Synthesis of α-Tertiary Amines via Radical Strategies

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(1), С. 22 - 22

Опубликована: Янв. 1, 2025

Язык: Английский

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Copper‐Catalyzed Oxidative C─N Coupling of Carbazoles with Arylglyoxal Hydrates

ChemistrySelect, Год журнала: 2025, Номер 10(19)

Опубликована: Май 1, 2025

Abstract In this study, a highly efficient Cu‐catalysed oxidative C─N coupling reaction was developed, which successfully achieved the of carbazole with aryl ketone aldehyde hydrates, showing wide range substrate applicability and good functional group tolerance. This method provides novel approach to synthesising diketones elucidates potential mechanism, thus offering significant tool for compounds demonstrating considerable application.

Язык: Английский

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Catalytic Enantioselective Nucleophilic Amination of α-Halo Carbonyl Compounds with Free Amines

Journal of the American Chemical Society, Год журнала: 2024, Номер 147(1), С. 576 - 584

Опубликована: Дек. 26, 2024

Catalytic enantioselective substitution of the readily available racemic α-halo carbonyl compounds by nitrogen nucleophiles represents one most convenient and direct approaches to access enantioenriched α-amino compounds. Distinct from two strategies involving radicals enolate ions, herein we have developed a new protocol featuring an electronically opposite way weaken/cleave carbon–halogen bond. A suitable chiral anion-based catalyst enables effective asymmetric control over key positively charged intermediates. This not only allows free amines serve as but also permits different types (ketones, esters, amides) participate in C–N bond formation, thereby providing valuable complement known that are limited certain substrates and/or nucleophiles. Preliminary studies indicated SN2 pathway is operational kinetic resolution involved.

Язык: Английский

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Recent progress in asymmetric radical reactions enabled by chiral iron catalysts

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

In this highlight, we discuss recently developed chiral iron catalysts and their application in radical asymmetric reactions for the construction of axial or central chirality.

Язык: Английский

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Copper-Catalyzed Asymmetric C(sp³)–H Benzylation: Stereoselective Synthesis of Unnatural Aromatic Amino Acids

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 6, 2024

The general synthesis of chiral unnatural aromatic amino acids has rarely been reported. We herein describe a visible light-promoted copper-catalyzed enantioselective C(sp

Язык: Английский

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