Alkyl radicals from diacyl peroxides: metal-/base-/additive-free photocatalytic alkylation of N-heteroaromatics

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(20), P. 7971 - 7977

Published: Jan. 1, 2023

Alkyl diacyl peroxides were demonstrated to be efficient alkylating reagents for the visible-light-induced 4CzIPN-catalyzed direct C–H alkylation of N -heteroaromatics.

Language: Английский

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Switchable divergent di- or tricarboxylation of allylic alcohols with CO2

Chem, Journal Year: 2024, Volume and Issue: 10(3), P. 938 - 951

Published: Jan. 10, 2024

Language: Английский

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Copper-Catalyzed Three-Component Photo-ATRA-Type Reaction for Asymmetric Intermolecular C–O Coupling

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(17), P. 10925 - 10937

Published: Aug. 22, 2022

Atom transfer radical addition (ATRA) reaction of alkenes has had a significant impact on the field difunctionalization alkenes. Particularly, in three-component photo-ATRA-type processes, rich chemical space and structural diversity could be achieved by smart combination redox-active precursors third coupling components (e.g., halides, C-, N-, O-nucleophiles) under mild conditions. However, inherent complicated mechanisms involving chain or outer-sphere SET incipient intermediates have led to dearth general catalytic methods for highly enantioselective variants, especially those regarding asymmetric intermolecular C–O bond formation. Here, we report visible-light-induced copper-catalyzed with oxime esters carboxylic acids. In this process, cross-coupling between sp3-hybridized carbon radicals acids was enabled formation an aryl π-bond-engaged [σ + π]-copper complex. This working hypothesis renders naphthyl extended conjugation suitable substrates allows good stereocontrol. exhibits broad substrate scope high functional group tolerance respect each component, giving desired products generally yields enantioselectivity (>70 examples; up 97% ee). Preliminary experimental computational studies are also performed gain insight into mechanism stereoregulatory elements. finding provides promising platform development other benzylic-type radical-based reactions.

Language: Английский

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Palladium-Catalyzed Carbonylations: Application in Complex Natural Product Total Synthesis and Recent Developments

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(8), P. 4925 - 4941

Published: Jan. 27, 2023

Carbon monoxide is a cheap and abundant C1 building block that can be readily incorporated into organic molecules to rapidly build structural complexity. In this Perspective, we outline several recent (since 2015) examples of palladium-catalyzed carbonylations in streamlining complex natural product total synthesis highlight the strategic importance these carbonylation reactions corresponding synthesis. The selected include spinosyn A, callyspongiolide, perseanol, schizozygane alkaloids, cephanolides, bisdehydroneostemoninine related stemona alkaloids. We also provide our perspective about advancements future developments carbonylations.

Language: Английский

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Photoinduced Five‐Component Radical Relay Aminocarbonylation of Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)

Published: Aug. 24, 2023

Radical single carbonylation reactions with CO constitute a direct and robust strategy toward various carbonyl compounds from readily available chemicals, have been extensively studied over the past decades. However, realizing highly selective catalytic systems for controlled radical double has remained substantial challenge, particularly more advanced multicomponent variants, despite their great potential value. Herein, we report visible-light-driven relay five-component aminocarbonylation reaction of unactivated alkenes using under metal-free conditions. This protocol provides access to valuable γ-trifluoromethyl α-ketoamides good yields high chemoselectivity. Crucial was identification distinct dual roles amine coupling partners, sequentially acting as electron donors formation photoactive donor-acceptor (EDA) complexes precursors then acceptor via nitrogen cations form carbamoyl radicals. Cross-coupling radicals acyl that are formed in an alkene-based process affords products.

Language: Английский

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Visible-Light-Promoted α-C(sp³)–H Amination of Ethers with Azoles and Amides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(4), P. 933 - 938

Published: Jan. 19, 2024

A visible-light-induced highly efficient C(sp3)–H amination of ethers with amides and azoles has been presented under mild conditions via a nitrogen- carbon-centered radical coupling process. This protocol successfully utilizes 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) tert-butyl nitrite (TBN) as cocatalysts to deliver the aminated products aerobic conditions. Notably, developed reaction features corresponding in good yields (up 93%) wide substrate scope. The mechanistic study indicates that C–N bond formation proceeds direct cross-coupling Preliminary biological activity analysis resulting have selective inhibitory on osteosarcoma (OS) cell lines are promising for use hits drug discovery.

Language: Английский

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Synchronous recognition of amines in oxidative carbonylation toward unsymmetrical ureas

Science, Journal Year: 2024, Volume and Issue: 386(6723), P. 776 - 782

Published: Nov. 14, 2024

Unsymmetrical ureas are commonly found in pharmaceuticals and bioactive compounds. However, devising strategies to introduce two distinct amines selectively the construction of unsymmetrical remains a challenge. In this work, we use synchronous recognition strategy that takes advantage radical nucleophilic activation discriminate between secondary primary amines. Specifically, copper catalyst preferentially oxidizes species, whereas cobalt carbonylates produce amides. Coupling these fragments by cooperative catalysis produces with high selectivity, as showcased modification 41 biologically active compounds six drugs.

Language: Английский

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Visible-light-driven EDA complex-promoted cascade cyclization to construct 4-cyanoalkyl isoquinoline-1,3-diones

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(21), P. 2958 - 2961

Published: Jan. 1, 2024

Visible-light-driven EDA complex-promoted ring-opening of cycloketone oxime esters to synthesise various 4-cyanoalkylated isoquinoline-1,3-diones with acryloylbenzamides was developed.

Language: Английский

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Copper-Catalyzed Selective Amino-alkoxycarbonylation of Unactivated Alkenes with CO

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

Published: Feb. 17, 2025

1,2-Amino-difunctionalization reactions of alkenes allow the efficient introduction different functional groups and rapid construction valuable functionalized amines. In this respect, we report a copper-catalyzed 1,2-amino-alkoxycarbonylation unactivated with CO alkylamine precursors in presence Lewis acid additive. The novel protocol allows direct access to β-amino derivatives from easily available starting materials. presented methods feature high chemo- regioselectivities, good group tolerance, substrate scope including diverse bioactive compounds drug-like molecules. Mechanistic studies indicate that additive is key realizing umpolung addition nucleophilic aminyl radicals electron-rich alkenes, which represents an elegant activation strategy for radicals.

Language: Английский

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Alkylboronic acids as alkylating agents: photoredox-catalyzed alkylation reactions assisted by K₃PO₄

Chemical Science, Journal Year: 2022, Volume and Issue: 13(45), P. 13466 - 13474

Published: Jan. 1, 2022

Despite the ubiquity of alkylboronic acids in organic synthesis, their utility as alkyl radical precursors visible-light-induced photocatalytic reactions is limited by high oxidation potentials. In this study, we demonstrated that an inorganophosphorus compound can modulate potentials so they act precursors. We propose a mechanism based on results fluorescence quenching experiments, electrochemical 11B and 31P NMR spectroscopy, other techniques. addition, describe simple reliable alkylation method has good functional group tolerance be used for direct C-B chlorination, cyanation, vinylation, alkynylation, allylation, well late-stage functionalization derivatized drug molecules. Notably, selectively activated presence boronic pinacol ester.

Language: Английский

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