Photocatalytic Enantioselective Hydrosulfonylation of α,β‐Unsaturated Carbonyls with Sulfonyl Chlorides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(46)

Опубликована: Окт. 2, 2023

This research explores the enantioselective hydrosulfonylation of various α,β-unsaturated carbonyl compounds via use visible light and redox-active chiral Ni-catalysis, facilitating synthesis enantioenriched α-chiral sulfones with remarkable enantioselectivity (exceeding 99 % ee). A significant challenge entails enhancing reactivity between metal-coordinated moderate electrophilic sulfonyl radicals, aiming to minimize background reactions. The success our approach stems from two distinctive attributes: 1) Cl-atom abstraction employed for radical generation chlorides, 2) single-electron reduction produce a key enolate Ni-complex. latter process appears enhance feasibility radical's addition electron-rich radical. An in-depth investigation into reaction mechanism, supported by both experimental observations theoretical analysis, offers insight intricate process. Moreover, versatility methodology is highlighted through its successful application in late-stage functionalization complex bioactive molecules, demonstrating practicality as strategy producing sulfones.

Язык: Английский

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Recent advances in dual photoredox/nickel catalyzed alkene carbofunctionalised reactions

Chemical Communications, Год журнала: 2024, Номер 60(68), С. 8946 - 8977

Опубликована: Янв. 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.

Язык: Английский

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Recent advances in catalytic asymmetric synthesis

Frontiers in Chemistry, Год журнала: 2024, Номер 12

Опубликована: Май 9, 2024

Asymmetric catalysis stands at the forefront of modern chemistry, serving as a cornerstone for efficient creation enantiopure chiral molecules characterized by their high selectivity. In this review, we delve into realm asymmetric catalytic reactions, which spans various methodologies, each contributing to broader landscape enantioselective synthesis molecules. Transition metals play central role catalysts wide range transformations with ligands such phosphines, N -heterocyclic carbenes (NHCs), etc., facilitating formation C-C and C-X bonds, enabling precise control over stereochemistry. Enantioselective photocatalytic reactions leverage power light driving force electrocatalysis has emerged sustainable approach, being both atom-efficient environmentally friendly, while offering versatile toolkit reductions oxidations. Biocatalysis relies on nature’s most catalysts, i.e., enzymes, provide exquisite selectivity, well tolerance diverse functional groups under mild conditions. Thus, enzymatic optical resolution, kinetic resolution dynamic have revolutionized production compounds. organocatalysis uses metal-free organocatalysts, consisting modular phosphorus, sulfur nitrogen components, remarkably transformations. Additionally, unlocking traditionally unreactive C-H bonds through selective functionalization expanded arsenal synthesis, atom-economical construction Incorporating flow chemistry been transformative, continuous systems reaction conditions, enhancing efficiency optimization. Researchers are increasingly adopting hybrid approaches that combine multiple strategies synergistically tackle complex synthetic challenges. This convergence holds great promise, propelling field forward in form. As these methodologies evolve complement one another, they push boundaries what can be accomplished leading discovery novel, highly may lead groundbreaking applications across industries.

Язык: Английский

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Red-light-mediated copper-catalyzed photoredox catalysis promotes regioselectivity switch in the difunctionalization of alkenes

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

Опубликована: Июнь 18, 2024

Abstract Controlling regioselectivity during difunctionalization of alkenes remains a significant challenge, particularly when the installation both functional groups involves radical processes. In this aspect, methodologies to install trifluoromethane (−CF 3 ) via have been explored, due importance moiety in pharmaceutical sectors; however, these existing reports are limited, most which affording only corresponding β-trifluoromethylated products. The main reason for limitation arises from fact that −CF group served as an initiator those reactions and predominantly preferred be installed at terminal (β) position alkene. On contrary, functionalization internal (α) would provide valuable products, but meticulous approach is necessary win switch. Intrigued by we here develop efficient regioselective strategy where α-position Molecular complexity achieved simultaneous insertion sulfonyl fragment (−SO 2 R) β-position. A precisely regulated sequence generation using red light-mediated photocatalysis facilitates switch position. Furthermore, demonstrates broad substrate scope industrial potential synthesis pharmaceuticals under mild reaction conditions.

Язык: Английский

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Ni-catalyzed enantioconvergent deoxygenative reductive cross-coupling of unactivated alkyl alcohols and aryl bromides

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

Опубликована: Март 28, 2024

Abstract Transition metal-catalyzed enantioconvergent cross-coupling of an alkyl precursor presents a promising method for producing enantioenriched C(sp 3 ) molecules. Because alcohol is ubiquitous and abundant family feedstock in nature, the direct reductive coupling aryl halide enables efficient access to valuable compounds. Although several strategies have been developed overcome high bond dissociation energy C − O bond, asymmetric pattern remains unknown. In this report, we describe realization deoxygenative unactivated (β-hydroxy ketone) bromide presence NHC activating agent. The approach can accommodate substituents various sizes functional groups, its synthetic potency demonstrated through gram scale reaction derivatizations into other compound families. Finally, apply our convergent synthesis four β-aryl ketones that are natural products or bioactive

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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Modular Access to Chiral Benzylamines via Ni/Photoredox-Catalyzed Multicomponent Cross-Electrophile Coupling

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 30, 2025

A Ni/photoredox dual-catalyzed multicomponent cross-electrophile coupling of N-vinyl amides with (hetero)aryl halides and (2°, 3°)-alkyl redox-active esters in the presence cheap reductant Hantzsch ester is reported here. This reductive protocol provides direct access to various synthetically challenging chiral α-arylamides good yields excellent enantioselectivities (up 99% ee, majority exceeding 97% ee), which can be further derived into primary secondary amines. Preliminary experimental studies shed light on potential catalytic pathways.

Язык: Английский

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Enantioselective Photoredox- and Cu-Catalyzed Cyanoalkylation of Styrenes via Deoxygenation of Alkoxyl Radicals with Organophosphorus Compounds(III)

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 11, 2025

The enantioselective cyanoalkylation of styrenes by a cooperative photoredox and copper catalysis system has been established, providing straightforward access to structurally diverse enantioenriched alkyl nitriles in good yields with excellent enantioselectivities under mild conditions via deoxygenation alkoxyl radicals organophosphorus compounds(III). In addition, the reaction features wide substrate scope functional group tolerance, resultant could be easily converted into series chiral carboxylic acids, amides, esters, etc.

Язык: Английский

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Deboronative cross-coupling enabled by nickel metallaphotoredox catalysis

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111053 - 111053

Опубликована: Март 1, 2025

Язык: Английский

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Nickel/photoredox dual catalyzed arylalkylation of nonactivated alkenes

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Ноя. 30, 2023

Alkene dicarbofunctionalization is an efficient strategy and operation-economic fashion for introducing complexity in molecules. A nickel/photoredox dual catalyzed arylalkylation of nonactivated alkenes the simultaneous construction one C(sp3)-C(sp3) bond C(sp3)-C(sp2) has been developed. The mild catalytic method provided valuable indanethylamine derivatives with wide substrate scope good functional group compatibility. An enantioselective was also achieved pyridine-oxazoline as a ligand. efficiency metallaphotoredox demonstrated concise synthesis pharmaceutically active compounds.

Язык: Английский

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