Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(16)

Опубликована: Янв. 29, 2024

Abstract We highlight key contributions in the field of direct radical C Ar − H (hetero)aromatic functionalization involving fluorinated radicals. A compilation Functional Group Transfer Reagents and their diverse activation mechanisms leading to release radicals are discussed. The substrate scope for each is analyzed classified into three categories according electronic properties substrates. Density functional theory computational analysis provides insights chemical reactivity several through electrophilicity nucleophilicity parameters. Theoretical reduction potentials also highlights remarkable correlation between oxidizing ability. It established that highly (e.g. ⋅OCF 3 ) capable engaging single‐electron transfer (SET) processes rather than addition, which good agreement with experimental literature data. scale, based on barrier addition these benzene elaborated using high accuracy DLPNO‐(U)CCSD(T) method.

Язык: Английский

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Pentafluorocyclopropanation of (Hetero)arenes Using Sulfonium Salts: Applications in Late‐Stage Functionalization

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(35)

Опубликована: Июль 4, 2023

The evaluation of the pentafluorocyclopropyl group as a chemotype in crop protection and medicinal chemistry has been hampered past by lack suitable methodologies that enable practical incorporation this moiety into advanced synthetic intermediates. Herein, we report gram-scale synthesis an unprecedented sulfonium salt, 5-(pentafluorocyclopropyl)dibenzothiophenium triflate, its use versatile reagent for photoinduced C-H pentafluorocyclopropylation broad series non-previously functionalized (hetero)arenes through radical mediated mechanism. scope potential benefits protocol developed are further demonstrated late-stage introduction unit biologically relevant molecules widely used pharmaceuticals.

Язык: Английский

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Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Angewandte Chemie, Год журнала: 2024, Номер 136(16)

Опубликована: Янв. 29, 2024

Abstract We highlight key contributions in the field of direct radical C Ar − H (hetero)aromatic functionalization involving fluorinated radicals. A compilation Functional Group Transfer Reagents and their diverse activation mechanisms leading to release radicals are discussed. The substrate scope for each is analyzed classified into three categories according electronic properties substrates. Density functional theory computational analysis provides insights chemical reactivity several through electrophilicity nucleophilicity parameters. Theoretical reduction potentials also highlights remarkable correlation between oxidizing ability. It established that highly (e.g. ⋅OCF 3 ) capable engaging single‐electron transfer (SET) processes rather than addition, which good agreement with experimental literature data. scale, based on barrier addition these benzene elaborated using high accuracy DLPNO‐(U)CCSD(T) method.

Язык: Английский

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Pentafluorocyclopropanation of (Hetero)arenes Using Sulfonium Salts: Applications in Late‐Stage Functionalization

Angewandte Chemie, Год журнала: 2023, Номер 135(35)

Опубликована: Июль 4, 2023

Abstract The evaluation of the pentafluorocyclopropyl group as a chemotype in crop protection and medicinal chemistry has been hampered past by lack suitable methodologies that enable practical incorporation this moiety into advanced synthetic intermediates. Herein, we report gram‐scale synthesis an unprecedented sulfonium salt, 5‐(pentafluorocyclopropyl)dibenzothiophenium triflate, its use versatile reagent for photoinduced C−H pentafluorocyclopropylation broad series non‐previously functionalized (hetero)arenes through radical mediated mechanism. scope potential benefits protocol developed are further demonstrated late‐stage introduction unit biologically relevant molecules widely used pharmaceuticals.

Язык: Английский

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Direct electrophilic and radical isoperfluoropropylation with i-C3F7-Iodine(III) reagent (PFPI reagent)

Communications Chemistry, Год журнала: 2023, Номер 6(1)

Опубликована: Авг. 24, 2023

The isoperfluoropropyl group (i-C3F7) is an emerging motif in pharmaceuticals, agrichemicals and functional materials. However, isoperfluoropropylated compounds remain largely underexplored, presumably due to the lack of efficient access these compounds. Herein, we disclose practical isoperfluoropropylation aromatic C-H bonds through invention a hypervalent-iodine-based reagent-PFPI reagent, that proceeds via Ag-X coupling process. activation PFPI reagent without any catalysts or additives was demonstrated synthesis electron-rich heterocycles, while its activity under photoredox catalysis shown non-activated arenes. Detailed mechanistic experiments DFT calculations revealed SET-induced concerted pathway reactions. In addition, unique conformation i-C3F7 products, involved intramolecular hydrogen bond investigated by X-ray single-crystal diffraction variable-temperature NMR experiments.

Язык: Английский

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Light promoted metal-free regio- and stereoselective isoperfluoropropylation of unactivated alkenes with an i-C₃F₇-iodine(iii) reagent

Organic Chemistry Frontiers, Год журнала: 2023, Номер 11(2), С. 370 - 379

Опубликована: Ноя. 24, 2023

A visible light promoted eco-friendly regio- and stereo-selective isoperfluoropropylation of various terminal alkenes alkynes with an i-C 3 F 7 -iodine( iii ) (PFPI) reagent.

Язык: Английский

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