BrCF2CN for photocatalytic cyanodifluoromethylation

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 7, 2025

Considering the unique electronic properties of CF2 and CN groups, CF2CN group has significant potential in drug agrochemical development, as well material sciences. However, incorporating a remains considerable challenge. In this work, we disclose use bromodifluoroacetonitrile (BrCF2CN), cost-effective readily available reagent, radical source for cyanodifluoromethylation alkyl alkenes, aryl alkynes, (hetero)arenes under photocatalytic conditions. This protocol demonstrates an exceptionally broad substrate scope remarkable tolerance to various functional groups. Notably, alkynes predominantly provides sterically hindered thermodynamically unfavorable outcome, (hetero)arene C-H bonds are directly amenable without pre-functionalization. Here, authors report (BrCF2CN)

Language: Английский

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Mechanochemical Synthesis of α‐halo Alkylboronic Esters

Advanced Science, Journal Year: 2024, Volume and Issue: 11(33)

Published: July 3, 2024

α-halo alkylboronic esters, acting as ambiphilic synthons, play a pivotal role versatile intermediates in fields like pharmaceutical science and organic chemistry. The sequential transformation of carbon-boron carbon-halogen bonds into broad range carbon-X allows for programmable bond formation, facilitating the incorporation multiple substituents at single position streamlining synthesis complex molecules. Nevertheless, synthetic potential these compounds is constrained by limited reaction patterns. Additionally, conventional methods often necessitate use bulk toxic solvents, exhibit sensitivity to air/moisture, rely on expensive metal catalysts, involve extended times. In this report, ball milling technique introduced that overcomes limitations, enabling external catalyst-free multicomponent coupling aryl diazonium salts, alkenes, simple halides. This approach offers general straightforward method obtaining diverse array thereby paving way extensive utilization synthons fine chemicals.

Language: Английский

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Cu-Catalyzed Three-Component Alkene Carboamination: Mechanistic Insights and Rational Design to Overcome Limitations

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(36), P. 25176 - 25189

Published: Aug. 28, 2024

Herein, we report mechanistic investigations into the Cu-catalyzed three-component carboamination of alkenes with α-halo carbonyls and aryl amines via an oxocarbenium intermediate. Monitoring reaction reveals formation transient atom transfer radical addition (ATRA) intermediates both electron-neutral deficient vinyl arenes as well unactivated alkenes. Based on our experimental studies density functional theory calculations, is generated through subsequent intramolecular substitution. Further, factors that dictate regioselectivity nucleophilic attack onto to afford γ-amino ester, γ-iminolactone, or γ-lactone are discussed. A strategy overcome scope limitation respect developed using insights gained herein. Finally, demonstrate under modified conditions, Cu catalyst enables ATRA between a variety alkyl halides arenes/α-olefins, present one-pot, two-step carbofunctionalization array nucleophiles ATRA/SN2.

Language: Английский

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Synthesis of α-Chloroboronic Esters via Photoredox-Catalyzed Chloro-Alkoxycarbonylation of Vinyl Boronic Esters

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

Published: March 9, 2025

α-Chloroboronic esters are a class of stable multifunctional molecules that show unique applications in pharmaceutical science and organic chemistry. Despite their apparent utility, the synthetic methods these compounds remain limited. Herein, novel strategy for efficient synthesis α-chloroboronic is developed via photoredox-catalyzed chloro-alkoxycarbonylation vinyl boronic esters. This features advantages high atom economy, environmental friendliness, excellent functional group compatibility was verified by cross-coupling variety free alcohols, oxalyl chlorides, Control experiments mechanistic studies indicate alkoxycarbonyl radical α-boryl carbocation key intermediates this transformation.

Language: Английский

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Copper-Catalyzed Reductive Alkylation of β-Acyl Allylic Thioethers with Alkyl Bromides to Access α-Branched Enones with Flexible Alkyl Chains

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

Published: April 15, 2025

Replacing alkyl organometallic reagents with bromides to achieve desulfurative alkylation of thioethers has been a long-standing challenge in functionalization organosulfur compounds. Herein, we report copper-catalyzed reductive tertiary β-acyl allylic sulfides α-carbonyl under mild reaction conditions. The accommodates broad substrate scope good functional group compatibility, providing direct route install diversified (sp3)-carbon quaternary centers at the position α-branched enones. Further synthetic applications this protocol have demonstrated scale-up experiments and late-stage modification products.

Language: Английский

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Copper-Catalyzed Three-Component 1,5-Carboamination of Vinylcyclopropanes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(22), P. 4621 - 4625

Published: May 29, 2024

The 1,5-copper-catalyzed carboamination of vinylcyclopropanes is presented. A carbon-centered radical, formed upon reduction an alkyl halide by Cu(I), adds across the alkene a vinylcyclopropane, triggering ring opening to generate benzylic which, finally, undergoes copper-mediated amination afford homoallylic amine. reaction occurs with outstanding regio- and good very diastereoselectivities. scope demonstrated respect all three components: halide, amine nucleophile. total 38 examples are presented average yield 60%.

Language: Английский

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Defluorinative Haloalkylation of Unactivated Alkenes Enabled by Dual Photoredox and Copper Catalysis

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13518 - 13529

Published: Sept. 10, 2024

A three-component defluorinative haloalkylation of alkenes with trifluoromethyl compounds and TBAX (X = Cl, Br) via dual photoredox/copper catalysis is reported. The mild conditions are compatible a wide array activated aromatics bearing diverse substituents, various nonactivated terminal internal alkenes, enabling straightforward access to synthetically valuable γ-gem-difluoroalkyl halides high efficiency. Mechanistic studies indicate that the [Cu] complexes not only serve as XAT catalysts but also facilitate SET reduction groups by photocatalysts. Additionally, resulting alkyl halide products can versatile conversion intermediates for synthesis range compounds.

Language: Английский

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A General Platform for Copper-Catalyzed Atom Transfer Radical Addition with Electron-Deficient Olefins

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

We disclose a broad platform for copper-catalyzed atom transfer radical addition (ATRA) of electron-deficient olefins. Catalytic Cu(dtbbpy)

Language: Английский

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