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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Photoinduced, Silver(I)-Mediated Synthesis of Ester-Substituted Fused Quinazolinones via Cascade Alkoxycarbonylation/Cyclization of Heterocycles Bearing Unactivated Alkenes

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(9), P. 5861 - 5874

Published: April 7, 2023

A new cascade alkoxycarbonylation/cyclization reaction of heterocycle-bearing unactivated alkenes is disclosed. The transformation mediated by silver carbonate under photoirradiation. This method provides efficient access to pharmaceutically valuable molecules and natural product analogues containing quinazolinone-fused esters. Furthermore, this protocol compatible with a variety quinazolinone-bearing alkyloxalyl chlorides that are readily prepared from abundant alcohols oxalyl chlorides.

Language: Английский

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Cu(OTf)₂-catalyzed multicomponent reactions

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 122 - 145

Published: Jan. 14, 2025

This review reports the achievements in copper(II) triflate-catalyzed processes concerning multicomponent reactions, applied to synthesis of acyclic and cyclic compounds. In particular, for heteropolycyclic systems mechanistic insights were outlined as well cycloaddition aza-Diels–Alder reactions included. These strategies have gained attention due their highly atom- step-economy, one-step multi-bond forming, mild reaction conditions, low cost easy handling.

Language: Английский

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Electrochemical Fe-catalyzed deoxygenative alkoxycarbonylation of imidazoheterocycles with carbazates

Synthetic Communications, Journal Year: 2025, Volume and Issue: 55(5), P. 422 - 432

Published: Feb. 2, 2025

Imidazo[1,2-a]pyridine derivatives possess widespread applications in the pharmaceutical industry and bioactive natural products. The diverse functionalization of this skeleton has attracted much attention from chemists. Herein, we reported an electrochemical deoxygenative alkoxycarbonylation imidazoheterocycles by using electrons as traceless oxidant under mild oxidant-free conditions. Notably, our strategy provided a green practical approach for introducing ester group into imidazo[1,2-a]pyridine employing easily available bench-stable carbazates source.

Language: Английский

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Copper-Catalyzed Regioselective 1,4-Sulfonyl Indolylation of 1,3-Dienes with Sulfonyl Chloride and Indoles

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

Published: Feb. 22, 2025

A copper-based catalytic system has been described to enable the efficient 1,4-sulfonylindolylation of 1,3-dienes with sulfonyl chloride and indoles. This protocol offers a practical method for synthesis allylsulfone-containing indole derivatives broad range compatible functionalities excellent chemo- regioselectivities. Mechanistic studies suggest that copper catalyst plays dual role initiating radicals prompting coupling in this conjugated diene-selective 1,4-difunctionalization strategy.

Language: Английский

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Electrochemical 1,2-Alkylarylation of Styrenes with Malonates and N-Heteroarenes via Direct C(sp³)–H/C(sp²)–H Functionalization

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

A general and atom-economical electrochemical dehydrogenative method for the intermolecular 1,2-alkylarylation of styrenes with malonates nucleophilic N-heteroarenes (including indoles pyrroles) has been developed. This transformation provides a regioselective route to construct highly valuable 1,1-diarylalkanes enabled by C(sp3)-H/C(sp2)-H functionalization under mild conditions, H2 is only theoretical byproduct. Mechanistic studies indicated that reaction proceeded through oxidative C(sp3)-H bond generate alkyl radical, radical addition across C═C bond, single electron oxidation C(sp2)-H cascades.

Language: Английский

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Visible-Light-Induced 4CzIPN-Catalyzed Alkylamination of Alkenes via Cyclobutanone Oxime Esters and Anilines

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

We disclosed an organophotoredox-catalyzed three-component oxidative radical-polar crossover strategy for constructing 1,2-alkylamination products. Cycloketone oxime derivatives were used as cyanoalkyl radical precursors and anilines the nucleophiles. This facile protocol shows a good reaction yield broad substrate scope.

Language: Английский

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Nitrogen-Based Organofluorine Functional Molecules: Synthesis and Applications

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern

Language: Английский

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Nitrogen-Centered Radicals Derived from Azidonucleosides

Molecules, Journal Year: 2024, Volume and Issue: 29(10), P. 2310 - 2310

Published: May 14, 2024

Azido-modified nucleosides have been extensively explored as substrates for click chemistry and the metabolic labeling of DNA RNA. These compounds are also interest precursors further synthetic elaboration therapeutic agents. This review discusses azidonucleosides related to generation nitrogen-centered radicals (NCRs) from azido groups that selectively inserted into nucleoside frame along with subsequent biological implications NCRs. For instance, critical role sulfinylimine radical generated during inhibition ribonucleotide reductases by 2′-azido-2′-deoxy pyrimidine nucleotides well NCRs radiation-produced (prehydrated aqueous) electrons discussed. Regio stereoselectivity incorporation an group (“radical arm”) selective under reductive conditions, which often produce same species observed upon ionization events due radiation and/or other oxidative conditions emphasized. nucleoside-modified than discussed but only direct relation same/similar derived azidonucleosides.

Language: Английский

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Photoinduced Ag-Mediated Azaspirocyclic Approach Involves Cyclization and Dearomatization

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 12, 2024

A visible-light-promoted protocol for azaspirocyclic synthesis from

Language: Английский

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