Continuous Flow Decarboxylative Monofluoroalkylation Enabled by Photoredox Catalysis

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 684 - 692

Published: Feb. 2, 2025

Herein, we report a scalable and mild strategy for the monofluoroalkylation of wide array Giese acceptors via visible-light-mediated photoredox catalysis in continuous flow. The use flow technology significantly enhances productivity scalability, whereas mildness conditions functional group tolerance are ensured by leveraging 4CzIPN, transition-metal-free organic photocatalyst. Structurally diverse secondary tertiary monofluoroalkyl radicals can thus be accessed from readily available α-monofluorocarboxylic acids. Given reaction conditions, this protocol is also amenable to late-stage functionalization biologically relevant molecules such as menthol, amantadine, bepotastine, estrone derivatives, rendering it suitable application drug discovery programs, which introduction fluorinated fragments highly sought after. This method was extended enable reductive multicomponent radical-polar crossover transformation rapidly increase complexity assembled architectures single synthetic operation.

Language: Английский

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Photoredox/NHC cooperative catalysis for alkylacylation of styrenes: An alternative method for the synthesis of γ-aminoketones

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: 156, P. 155450 - 155450

Published: Jan. 8, 2025

Language: Английский

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Carbamoylarylation of Alkenes with N-Aryl Oxamic Acids Involving 1,4-Aryl Migration Via C(aryl)–N Bond Cleavage

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 5972 - 5977

Published: April 4, 2024

We report carbamoylarylation of alkenes using N-aryl oxamic acid derivatives under visible-light irradiation. Reactions with carbamoyl radicals generated to afford Giese-type products or 3,4-dihydroquinolin-2(1H)-ones via ortho-radical addition an aryl amide moiety have been previously reported. However, this study reveals that the introduction a removable bulky group onto nitrogen atom acids facilitates radical alkenes, resulting in 1,4-aryl migration C(aryl)–N bond cleavage, thus affording arylpropanamides. Various such as acrylic and styrene derivatives, are successfully applied synthesis variety arylpropanamide including 1,4-dicarbonyl amides, forming two C–C bonds.

Language: Английский

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Synergistic Brønsted Base/Photoredox‐Catalyzed Three‐Component Coupling with Malonates to Synthesize δ‐Hydroxy Esters and δ‐Keto Esters

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(9), P. 957 - 962

Published: Jan. 18, 2024

Comprehensive Summary Multicomponent alkene 1,2‐dicarbofunctionalizations (DCFs) have emerged as a powerful strategy to rapidly incorporate both two carbon subunits across one C—C double bond in step for enhancing molecular complexity and diversity. To the best of our knowledge, there is only report on photoredox‐catalyzed three‐component DCFs with malonates through radical−radical cross‐coupling, while radical‐polar crossover (RPC)‐type were still rare. Herein, we describe redox‐neutral RPC‐type 1,2‐dialkylation styrenes aldehydes synergistic Brønsted base/photoredox catalysis system. This transition‐metal‐free provides an efficient clean approach broad variety δ‐hydroxy esters also features exceptionally mild conditions, wide compatibility substrate scope functional groups, high atomic economy. Moreover, 1,2‐alkylacylation from same starting materials was achieved one‐pot manner such coupling subsequent two‐electron oxidation process, providing set δ‐keto interest pharmaceutical research.

Language: Английский

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Visible-Light-Promoted Intermolecular β-Acyl Difunctionalization of Alkenes via Oxidative Radical-Polar Crossover

Organic Letters, Journal Year: 2023, Volume and Issue: 25(45), P. 8067 - 8071

Published: Nov. 8, 2023

A visible-light-induced β-acyl difunctionalization of alkenes with acyl oxime esters and various nucleophiles was developed to achieve molecular complexity from readily available raw materials via oxidative radical-polar crossover. variety nucleophiles, including NH-sulfoximines, indoles, indazole, trimethoxybenzene, were all effectively applicable the sustainable reaction system. The novel synthetic strategy features mild conditions, a broad substrate scope (39 examples), easy scale-up, excellent regioselectivity.

Language: Английский

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Discovery Process Chemistry: An Innovation Hub at the Interface of Academia, the Pharmaceutical Industry, and Contract Research Organizations

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 5, 2024

Abstract Discovery Process Chemistry (DPC) is an emerging intersectoral space that characterized by the development of new chemical reactions or syntheses enable efficient elucidation structure-activity relationships (SARs) and structure-property (SPRs) as well a rapid transition to process development. Drug discovery are accelerated such efforts this has led chemists in academia industry alike place increasing importance on these aims. In Short Review, we explore recent advances DPC impact it can have SAR/SPR interrogation downstream drug efforts. 1 Introduction 2 Enabling Interrogation with Bioisosteres 3 Couplings Diversifiable Reaction Partners 4 Late-Stage Functionalization 5 Conclusion Outlook

Language: Английский

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Multicomponent Reactions between Heteroatom Compounds and Unsaturated Compounds in Radical Reactions

Molecules, Journal Year: 2023, Volume and Issue: 28(17), P. 6356 - 6356

Published: Aug. 30, 2023

In this mini-review, we present our concepts for designing multicomponent reactions with reference to a series of sequential radical that have developed. Radical are well suited the design due their high functional group tolerance and low solvent sensitivity. We focused on photolysis interelement compounds heteroatom–heteroatom single bond, which readily generates heteroatom-centered radicals, studied photoinduced addition unsaturated compounds. First, background is described, basic methodology construction explained. Next, examples involving two one compound presented, as Furthermore, intramolecular cyclization processes described.

Language: Английский

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Recent advances in the synthesis of 3,3-disubstituted oxetanes

Advances in heterocyclic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 159 - 209

Published: Jan. 1, 2024

Language: Английский

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Visible-light-induced Synthesis of Organic Peroxides via Decarboxylative Couplings of Carboxylic Acids, Alkenes and tert-Butyl Hydroperoxide

Chemical Research in Chinese Universities, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 29, 2024

Language: Английский

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Crystal structure of 3-(tert-butyldiphenylsilyl)-1-(2,6-dichlorophenyl)-2,2-diphenylpropan-1-ol, C₃₇H₃₆Cl₂OSi

Zeitschrift für Kristallographie - New Crystal Structures, Journal Year: 2023, Volume and Issue: 239(1), P. 85 - 87

Published: Dec. 12, 2023

Abstract C 37 H 36 Cl 2 OSi, monoclinic P 1 / n (no. 14), a = 10.4363(14) Å, b 17.128(2) c 17.875(3) β 90.934(2)°, V 3194.8(8) Å 3 , Z 4, R gt ( F ) 0.0491, wR ref 0.1449, T 296.15 K.

Language: Английский

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