Rh(III)-Catalyzed Defluorinative [4 + 2] Annulation of N-Sulfonylarylamides with Ethyl 2-Diazo-3,3,3-trifluoropropanoate: Synthesis of 1,3,4-Functionalized Isoquinolines

Organic Letters, Год журнала: 2022, Номер 24(49), С. 8969 - 8974

Опубликована: Дек. 1, 2022

Using 2-diazo-3,3,3-trifluoropropanoate as a nontraditional two-carbon reaction partner, Rh(III)-catalyzed defluorinative [4 + 2] annulation for the synthesis of 1,3,4-functionalized isoquinolines was developed. The proceeds by sequential C-H carbenoid insertion, dual C-F bond cleavage/annulation, and N- to O-sulfonyl migration. resultant products were converted diverse 1,3,4-trisubstituted based on functionalization newly installed 1-sulfonate, 2-fluoro functional handles, and/or remaining ester motif.

Язык: Английский

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Organo-Photoredox Catalyzed gem-Difluoroallylation of Ketone-Derived Dihydroquinazolinones with α-Trifluoromethyl Alkenes via C(sp3)-C Bond and C(sp3)-F Bond Cleavage

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(27), С. 5561 - 5568

Опубликована: Янв. 1, 2024

An organo-photoredox catalyzed defluorinative alkylation of ketone-derived dihydroquinazolinones with α-trifluoromethyl alkenes is described, providing a facile access to diverse set gem -difluoroalkenes.

Язык: Английский

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Synthesis of mono-fluorinated heterocycles with a ring-junction nitrogen atom via Rh(iii)-catalyzed CF₃-carbenoid C–H functionalization and defluorinative annulation

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(6), С. 1544 - 1550

Опубликована: Янв. 1, 2023

A Rh-catalyzed two-fold C–F bond cleavage enabled [4 + 2] annulation reaction via CF 3 -carbenoid C–H functionalization of arenes with indoles or various classes azoles as the directing groups was developed.

Язык: Английский

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Visible-Light-Induced C–F and C–N Bond Cleavage for the Synthesis of gem-Difluoroalkenes

Organic Letters, Год журнала: 2022, Номер 24(36), С. 6566 - 6570

Опубликована: Сен. 2, 2022

Herein, we describe a novel and efficient photoredox catalytic radical addition/defluoroalkylation coupling reaction between primary amines trifluoromethyl-substituted alkenes. A series of gem-difluoroalkenes were synthesized via C–N bond cleavage α-3°, α-2°, α-1° under visible light irradiation. This is characterized by broad substrate scope good functional group tolerance.

Язык: Английский

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Organophotoredox and Hydrogen Atom Transfer Cocatalyzed C–H Alkylation of Quinoxalin-2(1H)-ones with Aldehydes, Amides, Alcohols, Ethers, or Cycloalkanes

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(21), С. 14580 - 14587

Опубликована: Окт. 7, 2022

Described is a mild method that merges organophotoredox catalysis with hydrogen atom transfer to enable C–H alkylation of quinoxalin-2(1H)-ones feedstock aldehydes, amides, alcohols, ethers, or cycloalkanes. This reaction occurred under environmentally benign and external oxidant-free conditions, providing general sustainable access various C3-alkylated quinoxalinone derivatives broad substituent diversity good functional group compatibility.

Язык: Английский

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Synthesis of gem‐difluoroalkenes via photoredox‐catalyzed defluoroaryloxymethylation of α‐trifluoromethyl alkenes

Bulletin of the Korean Chemical Society, Год журнала: 2022, Номер 44(1), С. 50 - 54

Опубликована: Ноя. 3, 2022

Abstract Herein, we present a novel method for the synthesis of gem ‐difluoroalkenes via visible‐light photoredox‐catalyzed defluoroaryloxymethylation α‐trifluoromethyl alkenes using α‐silyl ethers as aryloxymethyl radical precursors. This reaction shows good functional group tolerance and provides desired products in to excellent yields. Based on mechanistic studies, propose mechanism involving single‐electron oxidation an ether generate α‐aryloxymethyl radical.

Язык: Английский

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Divergent Synthesis of Benzo[4,5]imidazo[2,1-b][1,3]thiazines and α-Trifluoromethyl-β-arylthio Tertiary Alcohols from 2-Mercaptobenzimidazoles and α-CF₃ Alkenes

Organic Letters, Год журнала: 2024, Номер 26(44), С. 9610 - 9616

Опубликована: Окт. 25, 2024

An efficient and metal-free approach for the divergent synthesis of 2-fluoro-3-aryl-4H-benzo[4,5]imidazo[2,1-b][1,3]thiazines α-trifluoromethyl-β-arylthio tertiary alcohols from 2-mercaptoimidazoles α-CF3 alkenes has been developed. The chemoselectivity was well controlled by base or light; a series were afforded via base-mediated sequential SN2′- SNV-type reactions. Meanwhile, could be selectively achieved through visible-light-driven electron donor–acceptor (EDA) complex-initiated radical cascade thiolation/hydroxylation in absence base, transition metal, external photocatalyst.

Язык: Английский

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Solvent-Controllable C–F Bond Activation for Masked Formylation of α-Trifluoromethyl Alkenes via Organo-Photoredox Catalysis

The Journal of Organic Chemistry, Год журнала: 2023, Номер 89(1), С. 624 - 632

Опубликована: Дек. 20, 2023

A solvent-controllable organo-photoredox-catalyzed C–F bond activation for masked formylation of α-trifluoromethyl alkenes with low-priced 1,3-dioxolane as formyl radical equivalent has been described. Consequently, a diversity formylated gem-difluoroalkenes and monofluoroalkenes are constructed in moderate to high yields. This approach merits readily available starting materials, mild reaction conditions, broad substrate scope. The feasibility this highlighted by the one-pot formylation/hydrolysis sequence form γ,γ-difluoroallylic aldehydes late-stage modification pharmaceutical natural product derivatives.

Язык: Английский

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Organophotoredox-catalyzed ring-opening gem-difluoroallylation of nonstrained cycloalkanols

Molecular Catalysis, Год журнала: 2022, Номер 533, С. 112788 - 112788

Опубликована: Ноя. 4, 2022

Язык: Английский

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Visible Light Induced Selective Cleavage of Single C(sp3)-F Bond in Trifluoromethyl Groups Containing Compounds

Tetrahedron, Год журнала: 2024, Номер 163, С. 134155 - 134155

Опубликована: Июль 16, 2024

Язык: Английский

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