N‐Directed defluorinative γ‐C(sp3)−H allylation of sulfamate esters for synthesis of gem‐difluoroalkenes via photoredox catalysis
Sign Up to like & getrecommendations! Published in 2024 at "European Journal of Organic Chemistry"
DOI: 10.1002/ejoc.202400011
Abstract: gem‐Difluoroalkenes are unique structural motifs with important applications ranging from drugs to materials. Herein, we report a novel radical‐mediated defluorinative allylation of sulfamate esters with α‐trifluoromethyl alkenes through distal C(sp3)−H functionalization under photoredox conditions. The reaction… read more here.
Keywords: sp3; gem difluoroalkenes; allylation sulfamate; gem ... See more keywords
Palladium-Catalyzed Stereoselective Hydrodefluorination of Tetrasubstituted gem-Difluoroalkenes.
Sign Up to like & getrecommendations! Published in 2020 at "Organic letters"
DOI: 10.1021/acs.orglett.0c01813
Abstract: A highly stereoselective palladium(0)-catalyzed hydrodefluorination (HDF) of tetrasubstituted gem-difluoroalkenes is developed. By using catalytic Pd(PPh3)4 (2.5-5 mol %) and hydrosilane Me2PhSiH, various trisubstituted terminal (E)-monofluoroalkenes can be synthesized with excellent E/Z selectivity (>99:1) and good… read more here.
Keywords: tetrasubstituted gem; catalyzed stereoselective; gem difluoroalkenes; palladium catalyzed ... See more keywords
Photoredox-Catalyzed Difunctionalization of Unactivated Olefins for Synthesizing Lactam-Substituted gem-Difluoroalkenes.
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DOI: 10.1021/acs.orglett.1c03329
Abstract: Herein, the synthesis of lactam-substituted gem-difluoroalkenes has been developed through a photoredox-catalyzed radical cascade reaction. This developed photoredox-catalyzed, Brønsted base-assisted intramolecular 5-exo-trig cyclization/intermolecular radical addition/β-fluoride elimination reaction offers a simple method for producing lactam, carbamate,… read more here.
Keywords: gem difluoroalkenes; photoredox catalyzed; lactam substituted; substituted gem ... See more keywords
Highly Selective C-F Bond Functionalization of Tetrasubstituted gem-Difluoroalkenes and Trisubstituted Monofluoroalkenes Using Grignard Reagents.
Sign Up to like & getrecommendations! Published in 2022 at "Organic letters"
DOI: 10.1021/acs.orglett.2c01639
Abstract: We herein describe selective C-F bond functionalizations of tetrasubstituted gem-difluoroalkenes and trisubstituted monofluoroalkenes using Grignard reagents without the transition metal catalyst. β,β-Difluoroacrylates react with Grignard reagents under mild conditions to afford tetrasubstituted (E)-β-monofluoroacrylates. Experimental and… read more here.
Keywords: difluoroalkenes trisubstituted; grignard reagents; tetrasubstituted gem; gem difluoroalkenes ... See more keywords
Visible-Light-Induced C-F and C-N Bond Cleavage for the Synthesis of gem-Difluoroalkenes.
Sign Up to like & getrecommendations! Published in 2022 at "Organic letters"
DOI: 10.1021/acs.orglett.2c02528
Abstract: Herein, we describe a novel and efficient photoredox catalytic radical addition/defluoroalkylation coupling reaction between primary amines and trifluoromethyl-substituted alkenes. A series of gem-difluoroalkenes were synthesized via C-N bond cleavage of α-3°, α-2°, and α-1° amines… read more here.
Keywords: gem difluoroalkenes; bond cleavage; visible light;
Copper-Catalyzed Hydroamination of gem-Difluoroalkenes Access to Diversified α-Difluoromethyl Amines.
Sign Up to like & getrecommendations! Published in 2023 at "Organic letters"
DOI: 10.1021/acs.orglett.2c04278
Abstract: The difluoromethyl group (CF2H) is of great importance in medicinal chemistry. We report herein an efficient method for the synthesis of diversified α-difluoromethyl amines through copper-catalyzed hydroamination of gem-difluoroalkenes, where the C-N bond formed via… read more here.
Keywords: gem; gem difluoroalkenes; catalyzed hydroamination; difluoromethyl amines ... See more keywords
Chromium-Catalyzed Defluorinative Reductive Coupling of Aldehydes with gem-Difluoroalkenes.
Sign Up to like & getrecommendations! Published in 2023 at "Organic letters"
DOI: 10.1021/acs.orglett.3c00016
Abstract: Herein, a mild and convenient defluorinative reductive cross coupling of gem-difluoroalkenes with aliphatic aldehydes has been developed to afford diverse silyl-protected β-fluorinated allylic alcohols. The reaction is operationally simple and shows good functional group tolerance… read more here.
Keywords: catalyzed defluorinative; defluorinative reductive; gem difluoroalkenes; reductive coupling ... See more keywords
Electrochemical Difunctionalization of gem-Difluoroalkenes: A Metal-Free Synthesis of α-Difluoro(alkoxyl/azolated) Methylated Ethers.
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DOI: 10.1021/acs.orglett.3c01130
Abstract: A scalable electrochemical difunctionalization of gem-difluoroalkenes to structurally versatile difluoro motifs was achieved. This methodology features reagent-free conditions, good functional group tolerance, and a relatively broad substrate scope. Meanwhile, the electrolysis protocol is easy to… read more here.
Keywords: difunctionalization gem; gem difluoroalkenes; difluoro; electrochemical difunctionalization ... See more keywords
Addition of Carboxylic Acids to gem-Difluoroalkenes for the Synthesis of gem-Difluoromethylenated Compounds
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DOI: 10.1021/acs.orglett.4c00095
Abstract: We herein describe a straightforward protocol for the synthesis of carboxylic esters containing a gem-difluoromethylene unit. Readily available carboxylic acids can act as nucleophiles to add regioselectively to tetrasubstituted or trisubstituted β,β-difluoroacrylates (formal hydroacetoxylation) for… read more here.
Keywords: gem difluoroalkenes; acids gem; synthesis; gem ... See more keywords
Palladium-Catalyzed Defluorinative Alkylation of gem-Difluoroalkenes with Cyclopropanols: Stereoselective Synthesis of γ-Fluorinated γ,δ-Unsaturated Ketones.
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DOI: 10.1021/acs.orglett.4c01045
Abstract: A palladium-catalyzed defluorinative alkylation of gem-difluoroalkenes with cyclopropyl alcohols was developed. A range of γ-fluorinated γ,δ-unsaturated ketones were constructed in good yields with excellent stereoselectivities. In addition, by base-mediated intramolecular nucleophilic vinylic substitution (SNV), the… read more here.
Keywords: gem difluoroalkenes; palladium catalyzed; fluorinated unsaturated; defluorinative alkylation ... See more keywords
Zn-Mediated Fragmentation of N-Alkoxyphthalimides Enabling the Synthesis of gem-Difluoroalkenes.
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DOI: 10.1021/acs.orglett.4c01433
Abstract: Zn-mediated generation of alkoxyl radicals from N-alkoxyphthalimides emerged as an efficient approach for forming diverse and valuable alkyl radicals through β-scission or a hydrogen atom transfer process. The alkyl radical species can be further trapped… read more here.
Keywords: gem difluoroalkenes; enabling synthesis; mediated fragmentation; alkoxyphthalimides enabling ... See more keywords