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

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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Dual Nickel/Photoredox-Catalyzed Arylsulfonylation of Allenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(24), P. 5074 - 5081

Published: June 10, 2024

The nickel/photoredox dual catalysis system is an efficient conversion platform for the difunctionalization of unsaturated hydrocarbons. Herein, we disclose first nickel/photoredox-catalyzed intramolecular 1,2-arylsulfonylation allenes, which can accurately construct a C(sp2)–C(sp2) bond and C(sp3)–S bond. reaction exhibits excellent chemoselectivity regioselectivity, allowing modular conformations diverse series 3-sulfonylmethylbenzofuran derivatives. Control experiments showed that bipyridine ligand crucial formation stable σ-alkyl nickel intermediate, providing possibility sulfonyl radical insertion. Meanwhile, electrophilic facilitates further oxidative addition intermediate inhibits with allenes. In addition, control experiments, cyclic voltammetry tests, Stern–Volmer density functional theory calculations afford evidence Ni(0)/Ni(I)/Ni(II)/Ni(III) pathway in this 1,2-arylsulfonylation.

Language: Английский

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Recent advances in dual photoredox/nickel catalyzed alkene carbofunctionalised reactions

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(68), P. 8946 - 8977

Published: Jan. 1, 2024

Alkene carbofunctionalization reactions have great potential for synthesizing complex molecules and constructing structures in natural products medicinal chemistry. Recently, dual photoredox/nickel catalysis has emerged as a novel strategy alkene carbofunctionalization. Nickel offers numerous advantages over other transition metals, such cost-effectiveness, abundance, low toxicity, moreover, it many oxidation states. catalysts exhibit excellent catalytic activity photoredox/transition metal catalysis, facilitating the formation of carbon-carbon or carbon-heteroatom bonds organic transformations. This review highlights latest advancements photoredox/nickel-catalyzed carbofunctionalizations includes literature published from 2020 to 2024.

Language: Английский

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Copper/ruthenium relay catalysis enables 1,6-double chiral inductions with stereodivergence

Chemical Science, Journal Year: 2024, Volume and Issue: 15(26), P. 10135 - 10145

Published: Jan. 1, 2024

A stereodivergent synthesis of chiral ζ-hydroxy amino esters containing 1,6-stereocenters and a unique β,γ-unsaturation was developed through asymmetric Cu/Ru relay catalysis to conduct the borrowing hydrogenation/1,6-Michael addition protocol.

Language: Английский

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Unveiling Heavier Dihydropyridine Chalcogenol Esters in Metallaphotoredox Catalyst-Enabled Regioselective Hydrothio(seleno)carbonylation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Herein, aromaticity-driven thio(seleno)ester group transfer from novel 1,4-dihydropyridine thio(seleno)esters to alkene feedstocks is disclosed by merging palladium and photoredox catalysis. In this process, photoactivation of dihydropyridine integrated with regioselective hydrometalation alkenes, avoiding photoinduced Pd-C bond homolysis organopalladium intermediates. Additionally, a hydroselenocarbonylation an accomplished for the first time using bench-stable selenoester reagent. The activation mode thioesters has been illustrated detailed mechanistic studies, spectroscopic analysis, intermediate trapping, isotope labeling experiments.

Language: Английский

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Metallaphotoredox-Catalyzed Three-Component Asymmetric Cross-Electrophile Coupling for Chiral Boronate Synthesis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(20), P. 15790 - 15798

Published: Oct. 10, 2024

Here, we report a photoredox and nickel-catalyzed cross-electrophile coupling strategy for the asymmetric three-component 1,2-alkylarylation of vinyl boronates with (hetero)aryl bromides (2°, 3°)-alkyl redox-active esters in presence Hantzsch ester. With fluorinated pyridyl-substituted chiral biimidazoline ligand, this reaction enables straightforward access to wide variety synthetically valuable α-aryl from readily available starting materials. This features mild conditions, broad substrate generality, good functional group tolerance proceeds without using metal reductants or alkyl halides. Furthermore, alkenyl halides other electron-deficient alkenes such as acrylates phosphonates can be applied successfully. Preliminary mechanistic studies shed light on potential pathways roles organic amines.

Language: Английский

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Facile synthesis of alkylphosphonates from 4-alkyl-1,4-dihydropyridines via photoinduced formal deformylative phosphonylation

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(16), P. 4502 - 4507

Published: Jan. 1, 2024

A photoinduced formal deformylative phosphonylation utilizing easily available aldehydes was established, providing a practical synthetic route to alkylphosphonates from aliphatic aldehydes.

Language: Английский

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Ni-Catalyzed Desymmetric Radical Cross-Coupling Reaction to Access Axially Chiral Biaryls

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(18), P. 13860 - 13866

Published: Sept. 3, 2024

The synthesis of axially chiral biaryls continues to garner significant attention in the scientific community. In this work, we introduce a Ni-catalyzed desymmetrization strategy for prochiral dibromoarenes, conducted under mild reaction conditions and with good functional group tolerance. This method allows from readily available coupling partners, such as aldehydes, ethers, unactivated alkyl bromides. Moreover, has been successfully applied concise enantioenriched azulene-embedded [7]helicene, promising organic optoelectronics material.

Language: Английский

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Copper(I)‐Catalyzed Proto/Carboboration of Enyne Boronates for the Synthesis of Densely Substituted Diene Diboronates

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 12, 2024

Abstract A copper‐catalyzed carbo‐/protoboration of boryl enynes is disclosed, providing access to an array penta‐ and hexasubstituted diboryl dienes in a chemo‐, regio‐ stereoselective manner. All six positions the can be manipulated using this methodology. The diene boronates adopt skew conformation. An iterative Suzuki coupling products provided highly conjugated trienes tetraenes.

Language: Английский

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