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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Multicomponent Synthesis of Alkyl BCP-Heteroaryls via Electron Donor–Acceptor Complex Photoactivation under Mild Conditions

The Journal of Organic Chemistry, Год журнала: 2025, Номер 90(4), С. 1683 - 1696

Опубликована: Янв. 17, 2025

In the vanguard of sustainable chemistry, pursuit efficient pathways for synthesis alkyl bicyclo[1.1.1]pentane-heteroaryls has captured attention scientific vanguard. We herein report a groundbreaking and eco-conscious multicomponent coupling reaction that paves way alkylation heteroarylation [1.1.1]propellane, process uniquely enabled by photochemical prowess an electron donor–acceptor (EDA) complex. This method is distinguished its minimalist yet powerful approach: devoid transition metals, additives, photosensitizers. Its universality further exemplified seamless compatibility broad spectrum halides heteroarenes under standardized conditions, heralding new era synthetic versatility. The method's practicality underscored capacity late-stage modification pharmaceuticals, offering transformative tool enhancement existing drug molecules. Moreover, facile derivatization synthesized products underscores adaptability potential diverse applications. Our mechanistic studies have elucidated underlying radical-relay pathway, pinpointing pivotal role EDA complex in initiating transformation. discovery not only enriches our fundamental understanding but also opens avenues strategic optimization.

Язык: Английский

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Electron-Donor-Mediated Divergent Transformation of Br–R_F via EDA Complex for the Synthesis of Fluorine-Containing Oxindoles and Amides

Organic Letters, Год журнала: 2024, Номер 26(46), С. 9990 - 9995

Опубликована: Ноя. 11, 2024

We have developed an unprecedented electron-donor-controlled divergent reaction between

Язык: Английский

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Copper-Catalyzed Diastereoselective Addition of a [1,1,1]Propellane Dimer to N-tert-Butanesulfinyl Aldimines

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 21, 2025

[1,1,1]Propellane is typically used as a building block for the construction of bicyclo[1,1,1]pentanes and cyclobutanes. In this work, diverse chiral bi(methylenecyclobutylidene) complexes were synthesized by diastereoselective addition [1,1,1]propellane dimer to N-tert-butanesulfinyl aldimines in presence copper bipyridine. Density functional theory calculations revealed that both step regeneration catalyst contributed generation favored (Ss,S,S)-diastereomer.

Язык: Английский

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Photoredox-catalyzed three-component alkylation of glycine derivatives and peptides via a site-selective 1,5-hydrogen atom transfer cascade

Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

We report a visible-light-mediated three-component reaction via 1,5-HAT combined with site-selective remote C(sp 3 )–H cross-coupling reactions of alkenes alkyl radicals for the α-C(sp alkylation glycine derivatives and peptides.

Язык: Английский

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Site-Specific Radical Alkylation of Aryl Cyanide: Visible-Light, Photoredox-Catalyzed, Three-Component Arylalkylation of [1.1.1]Propellane

Organic Letters, Год журнала: 2024, Номер 26(36), С. 7769 - 7773

Опубликована: Сен. 4, 2024

We report herein a three-component radical arylalkylation of [1.1.1]propellane toward the synthesis aryl-substituted bicyclo[1.1.1]pentane derivatives. The use electron-deficient aryl cyanide as an group source not only reduces energy barrier arylation nucleophilic alkyl species, but also suppresses electrophilic Friedel-Crafts alkylation process, enabling present site-selective arylalkylation.

Язык: Английский

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Photoinduced Phosphoniumation of Aryl Halides and Arylthianthrenium Salts via an Electron Donor–Acceptor Complex

Organic Letters, Год журнала: 2024, Номер 26(36), С. 7751 - 7756

Опубликована: Сен. 5, 2024

Owing to their remarkable practicality and utility, phosphonium salts have attracted substantial interest are widely applied in critical areas, such as medicine, materials science, catalysis. Herein, we developed a facile photocatalyst/metal-free synthetic strategy for the preparation of utilizing aryl halides/arylthianthrenium radical precursors. This approach is disclosed undergo an efficient light-induced electron donor-acceptor pathway, facilitating synthesis structurally diverse range salts.

Язык: Английский

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Benzyl Alcohol Functionalization of [1.1.1]Propellane with Alkanes and Aldehydes

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Окт. 21, 2024

Bicyclo[1.1.1]pentanes (BCPs) play a crucial role in drug discovery research as C(sp

Язык: Английский

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Stabilized Carbon Radical‐Mediated Assembly of Arylthianthrenium Salts, Alkenes and Amino Acid/Peptide Derivatives

Advanced Science, Год журнала: 2024, Номер 12(2)

Опубликована: Ноя. 21, 2024

Abstract Efficiently assembling amino acids and peptides with bioactive molecules facilitates the modular streamlined synthesis of a diverse library peptide‐related compounds. Particularly notable is their application in pharmaceutical development, leveraging site‐selective late‐stage functionalization. Here, visible light‐induced three‐component reaction involving arylthianthrenium salts, acid/peptide derivatives, alkenes are introduced. This approach utilizes captodatively‐stabilized carbon radicals to enable radical‐radical C─C coupling, effectively constructing complex molecules. method offers promising alternative route for peptide‐derived bio‐relevant compounds

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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