Three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals

Chemical Communications, Год журнала: 2021, Номер 58(6), С. 730 - 746

Опубликована: Дек. 8, 2021

This article provides a comprehensive perspective on three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals, which generated from structurally diverse electrophilic and nucleophilic precursors under mild conditions.

Язык: Английский

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Photoinduced Vicinal 1,2-Difunctionalization of Olefins for the Synthesis of Alkyl Sulfonamides

Organic Letters, Год журнала: 2023, Номер 25(6), С. 1014 - 1019

Опубликована: Фев. 6, 2023

Alkyl sulfonamides are an important class of bioactive molecules. Historical syntheses have relied on multistep sequences incorporating harsh reaction conditions. Photochemical methods been limited to hydrosulfamoylation, installing only one substituent across olefin. Herein, radical/polar crossover (RPC) is used establish the first multicomponent 1,2-difunctionalization a sulfonamide moiety and second partner. This protocol, exemplified range olefins, utilizes various commercial sulfamoyl chlorides organotrifluoroborates as coupling partners.

Язык: Английский

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Ni-Catalyzed Regioselective Alkylarylation of Unactivated Alkenes in Amines Enabled by Cooperative Ligand Effects of Nitriles and Electron-Deficient Alkenes

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(2), С. 1667 - 1676

Опубликована: Янв. 7, 2025

We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides alkylzinc reagents. The reaction is enabled by amine coordination can use all primary, secondary, tertiary amines. constructs two new C(sp3)-C(sp3) C(sp3)-C(sp2) bonds produces δ- ε-arylamines C(sp3)-branching at the γ- δ-positions. A variety heteroaryl iodides both primary secondary reagents be used as coupling carbon sources. Mechanistic studies suggest that cooperative effect organic nitriles electron-deficient (EDAs) ligands.

Язык: Английский

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Recent Advances in Mono‐ and Difunctionalization of Unactivated Olefins

Asian Journal of Organic Chemistry, Год журнала: 2021, Номер 10(12), С. 3201 - 3232

Опубликована: Ноя. 5, 2021

Abstract Olefins are synthetically useful building blocks in modern organic synthesis. Direct functionalization of olefins; represent one the most explored transformations synthetic chemistry due to their easy availability and reactivity towards large number reactants affording diverse range compounds. In recent times, development new protocols for olefins is a growing realm. A plethora olefin methodologies have been reported literature through ionic free radical mechanisms including single electron transfer (SET) last two decades. This review gives an overview mono‐ difunctionalization unactivated olefins, with emphasis on mechanistic details.

Язык: Английский

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From Styrenes to Fluorinated Benzyl Bromides: A Photoinduced Difunctionalization via Atom Transfer Radical Addition

Organic Letters, Год журнала: 2022, Номер 24(26), С. 4750 - 4755

Опубликована: Июнь 29, 2022

An operationally simple and practical method is disclosed to achieve the difunctionalization of styrenes, generating fluorinated benzyl bromides via a photoinduced atom transfer radical addition process. The developed mild, atom-economical, cost-effective, employs very low photocatalyst loading (1000 ppm), highly compatible with broad range functional groups on styrene. versatility demonstrated through their derivatization variety valuable compounds.

Язык: Английский

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Recent Advances in Photoredox-Catalyzed Difunctionalization of Alkenes

Catalysts, Год журнала: 2023, Номер 13(7), С. 1056 - 1056

Опубликована: Июнь 30, 2023

Alkenes and their related analogs are ideal starting materials for organic synthesis, the selective difunctionalization of alkenes, which allows simultaneous introduction two neighboring bonds, has gained considerable attention in recent years. In particular, photoredox-catalyzed alkenes also been accomplished, regarded as an increasingly powerful tool synthesis miscellaneous interesting molecular scaffolds environmentally benign economical manner. Several exquisite strategies have developed to facilitate this transformation, such photosensitizer-catalyzed redox reactions, electron donor-acceptor (EDA) complexes-mediated photoreactions, atom transfer radical addition (ATRA) reactions. This literature review briefly describes most key progress on 1,2-difunctionalization various structurally diverse including 1,2-dicarbofunctionalization, 1,2-carboheterofunctionalization, 1,2-diheterofunctionalization, with a special emphasis mechanistic details.

Язык: Английский

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Modular and Practical 1,2‐Aryl(Alkenyl) Heteroatom Functionalization of Alkenes through Iron/Photoredox Dual Catalysis**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(44)

Опубликована: Сен. 13, 2023

Abstract Efficient methods for synthesizing 1,2‐aryl(alkenyl) heteroatomic cores, encompassing heteroatoms such as nitrogen, oxygen, sulfur, and halogens, are of significant importance in medicinal chemistry pharmaceutical research. In this study, we present a mild, versatile practical photoredox/iron dual catalytic system that enables access to highly privileged pharmacophores with exceptional efficiency site selectivity. Our approach exhibits an extensive scope, allowing the direct utilization wide range commodity or commercially available (hetero)arenes well activated unactivated alkenes diverse functional groups, drug scaffolds, natural product motifs substrates. By merging iron catalysis photoredox cycle, vast array alkene functionalization products incorporate neighboring azido, amino, halo, thiocyano nitrooxy group were secured. The scalability ability rapid synthesize numerous bioactive small molecules from readily starting materials highlight utility protocol.

Язык: Английский

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A free-radical design featuring an intramolecular migration for a synthetically versatile alkyl–(hetero)arylation of simple olefins

Chemical Science, Год журнала: 2024, Номер 15(11), С. 4031 - 4040

Опубликована: Янв. 1, 2024

A free-radical approach featuring an intramolecular aryl migration has significantly expanded the scope for alkyl–(hetero)arylation of simple olefins. It was also leveraged as key step in a new synthesis recently approved pharmaceutical.

Язык: Английский

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Cobalt Hydride-Catalyzed Hydroalkynylation of Alkenes with Alkynyl Trifluoroborates

ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9294 - 9301

Опубликована: Июнь 4, 2024

A cobalt-catalyzed hydroalkynylation of alkenes with alkynyl trifluoroborates is described, proceeding through a cobalt hydride-mediated radical-polar crossover metal hydrogen-atom-transfer process. This method affords structurally diverse alkynyl-containing compounds in high yields under mild conditions and features wide substrate scope, good functional group tolerance, suitability for late-stage functionalization relatively complex natural products bioactive molecules. Expanding the scope to alkenyltrifluoroborate salts further increases utility developed methodology. approach paves an alternative route radical-involved alkynylation alkenylation reactions nucleophilic alkynyl/alkenyl reagents.

Язык: Английский

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Radical Redox Annulations: A General Light-Driven Method for the Synthesis of Saturated Heterocycles

ACS Catalysis, Год журнала: 2022, Номер 12(21), С. 13732 - 13740

Опубликована: Окт. 26, 2022

We introduce here a two-component annulation strategy that provides access to diverse collection of five- and six-membered saturated heterocycles from aryl alkenes family redox-active radical precursors bearing tethered nucleophiles. This transformation is mediated by combination an Ir(III) photocatalyst Brønsted acid under visible-light irradiation. A reductive proton-coupled electron transfer generates reactive which undergoes addition alkene. Then, oxidative radical-polar crossover step leading carbocation formation followed ring closure through cyclization the nucleophile. wide range are easily accessible, including pyrrolidines, piperidines, tetrahydrofurans, morpholines, δ-valerolactones, dioxanones. demonstrate scope this approach broad structural variation both reaction components. method amenable gram-scale preparation complex fragment coupling.

Язык: Английский

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