Difluoroalkylation of Anilines via Photoinduced Methods

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(17), P. 12585 - 12596

Published: Aug. 16, 2023

The development of sustainable and mild protocols for the fluoroalkylation organic backbones is current interest in chemical synthesis. Herein, we present operationally simple practical transition-metal-free methods preparation difluoroalkyl anilines. First, a visible-light organophotocatalytic system working via oxidative quenching described, providing access to wide range anilines under conditions. In addition, formation an unprecedented electron donor-acceptor (EDA) complex between ethyl difluoroiodoacetate reported exploited as alternative, efficient, straightforward strategy prepare derivatives.

Language: Английский

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Photocatalytic α‐Difluoroalkoxyketones Synthesis via Radical Intermolecular Alkoxylation of Difluoroenol Silyl Ethers

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(16), P. 3500 - 3504

Published: June 27, 2024

Abstract We present a metal‐free photocatalytic approach for the synthesis of difluoroalkoxylatedketones. This strategy involves generation alkoxyl radicals from pyridinium salts upon activity catalytic electron‐donor‐acceptor (EDA) complex. mild process tolerates several functional groups and can be scaled up to gram scale. Diverse products manipulations accounts versatility obtained fluorinated products, highlighting synthetic usefulness this method.

Language: Английский

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Light‐Driven Synthesis and Functionalization of Bicycloalkanes, Cubanes and Related Bioisosteres

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(14)

Published: Jan. 5, 2024

Abstract Bicycloalkanes, cubanes and their structural analogues have emerged as bioisosteres of (hetero)arenes. To meet increasing demand, the chemical community has developed a plethora novel synthetic methods. In this review, we assess progress made in field light‐driven construction functionalization such relevant molecules. We focused on diverse targets, well reaction processes giving access to: (i) [1.1.1]‐bicyclopentanes (BCPs); (ii) [2.2.1]‐bicyclohexanes (BCHs); (iii) [3.1.1]‐bicycloheptanes (BCHeps); (iv) cubanes; other structurally related scaffolds. Finally, future perspectives dealing with identification manifolds to new functionalized bioisosteric units are discussed.

Language: Английский

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Metal-free and visible-light-mediated method enables the synthesis of olefins from ketones

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

Published: Feb. 1, 2024

Direct synthesis of olefins continues to attract stellar attention due the high importance olefins. In this context, wide availability ketones, directly from ketones provides a straightforward route. Considering this, via formation donor/donor type carbenes has been developed which leads efficient versatile by using metal-free strategy. This approach features mild reaction conditions and exhibits broad substrate scope when biomass-derived solvent as green media is used. The practical utility demonstrated late-stage modifications even scaling up 20 grams scale. At end, mechanistic investigations density functional theory studies clearly proved carbenes, examined necessity all reagents effect light in system.

Language: Английский

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Direct Synthesis of 2-Hydroxytrifluoroethylacetophenones via Organophotoredox-Mediated Net-Neutral Radical/Polar Crossover

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(16), P. 11682 - 11692

Published: Aug. 1, 2024

Alkene difunctionalization is a very attractive tool in synthetic organic chemistry. Herein, we disclose an operationally and practically simple method to access 2-hydroxytrifluoroethylacetophenones from styrene derivatives via photoredox catalysis. This light-mediated transformation promotes the generation of 1-hydroxy-2,2,2-trifluoroethyl carbon-centered radical as key synthon, which undergoes Giese addition with styrenes followed by Kornblum oxidation process. The presented not only mild cost-effective, but also utilizes photocatalyst DMSO oxidant. Experimental investigations support operative mechanism net-neutral radical/polar crossover.

Language: Английский

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Photoreduction of Trifluoromethyl Group: Lithium Ion Assisted Fluoride‐Coupled Electron Transfer from EDA Complex

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(33)

Published: April 11, 2024

Photoinduced single-electron reduction is an efficient method for the mono-selective activation of C-F bond on a trifluoromethyl group to construct difluoroalkyl group. We have developed electron-donor-acceptor (EDA) complex mediated transfer (EDA-SET) α,α,α-trifluoromethyl arenes in presence lithium salt give α,α-difluoroalkylarenes. The was realized by iodide and triethylamine, two common feedstock reagents. Mechanistic studies revealed generation α,α-difluoromethyl radical defluorination, followed addition alkenes. Lithium interacted with fluorine atom promote photoinduced EDA complex. Computational indicated that lithium-assisted defluorination occurred concertedly. call this phenomenon fluoride-coupled electron (FCET). FCET novel approach synthesis organofluorine compounds.

Language: Английский

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Difluorocarbene Enables Modular Synthesis of Difluoroalkylated Bicyclopentanes

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

Published: Aug. 21, 2024

Abstract A straightforward method for the synthesis of difluoroalkylated bicyclopentanes (BCPs) from [1.1.1]propellane (TCP) through a stepwise procedure has been developed. This process involves nucleophilic addition organozinc or ArMgBr reagents to TCP, followed by reaction with difluorocarbene generate BCP substituted difluoroalkylzinc species, which subsequently couple electrophiles, including allyl/propargyl bromides, (hetero)aryl disulfides, and proton, provide wide range BCPs that otherwise are difficult access conventional methods. The transformations resulting products demonstrate synthetic utility this modular synthesis.

Language: Английский

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Synthetic Strategies and Applications of Fluorine‐Containing Bridged Bicyclic Compounds

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(43)

Published: Aug. 5, 2024

Abstract Bridged bicyclic compounds (BBCs) have recently emerged as effective 3D‐isosteres of planar aryl and heteroaryl rings. Current synthetic endeavours are devoted to accessing these complex structures bearing functionalities in different positions the aliphatic Of particular interest is incorporation F‐containing motifs, since it allows generation isosteric units with improved physicochemical properties, including lipophilicity, water solubility, or oxidative resistance.

Language: Английский

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Controlled oligomerization of [1.1.1]propellane through radical polarity matching: selective synthesis of SF₅- and CF₃SF₄-containing [2]staffanes

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 3134 - 3143

Published: Nov. 29, 2024

Selectivity in radical chain oligomerizations involving [1.1.1]propellane – i.e., to make [ n ]staffanes has been notoriously challenging control when > 1 is desired. Herein, we report selective syntheses of SF 5 - and CF 3 4 -containing [2]staffanes from Cl Cl, demonstrating cases whereby oligomerization preferentially truncated after incorporation two bicyclopentane (BCP) units. Synthetic computational studies suggest this phenomenon can be attributed alternating polarity matching. In addition, single-crystal X-ray diffraction (SC-XRD) data reveal structurally interesting features the [2]staffane solid state.

Language: Английский

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Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF₅‐Cyclobutanes

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(19)

Published: Jan. 18, 2024

Abstract The first assortment of achiral pentafluorosulfanylated cyclobutanes (SF 5 ‐CBs) are now synthetically accessible through strain‐release functionalization [1.1.0]bicyclobutanes (BCBs) using SF Cl. Methods for both chloropentafluorosulfanylation and hydropentafluorosulfanylation sulfone‐based BCBs detailed herein, as well proof‐of‐concept that the logic extends to tetrafluoro(aryl)sulfanylation, tetrafluoro(trifluoromethyl)sulfanylation, three‐component pentafluorosulfanylation reactions. methods presented enable isolation syn anti isomers ‐CBs, but we also demonstrate this innate selectivity can be overridden in chloropentafluorosulfanylation; is, an ‐stereoselective variant Cl addition across achieved by inexpensive copper salt additives. Considering group CBs have been employed individually nonclassical bioisosteres, structural aspects these unique ‐CB “hybrid isosteres” were then contextualized SC‐XRD. From a mechanistic standpoint, ostensibly proceeds curious polarity mismatch electrophilic radicals sites BCBs. Upon examining carbonyl‐containing BCBs, observed rare instances whereby radical 1‐position BCB occurs. nature key C(sp 3 )−SF bond formation step – among other features disclose was investigated experimentally with DFT calculations. Lastly, compatibility ‐CBs various downstream functionalizations.

Language: Английский

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