Visible-Light-Induced Defluorinative α-C(sp³)–H Alkylation for the Synthesis of gem-Difluoroallylated α-Trifluoromethylamines

Organic Letters, Год журнала: 2023, Номер 25(51), С. 9124 - 9129

Опубликована: Ноя. 17, 2023

Herein, we describe a novel and efficient photoredox catalytic Cα radical addition/defluoroalkylation coupling reaction between α-trifluoromethyl alkenes N-trifluoroethyl hydroxylamine. A series of gem-difluoroallylated α-trifluoromethylamines were synthesized by the addition enabled 1,2-H shift in situ-generated radical. Notably, this protocol is distinguished its mild conditions, easy operation, excellent functional group tolerability.

Язык: Английский

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Alkene 1,1-difunctionalizations via organometallic-radical relay

Nature Catalysis, Год журнала: 2023, Номер 6(11), С. 1030 - 1041

Опубликована: Сен. 28, 2023

Язык: Английский

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Stereoselective hydrodefluorination of CF₃-substituted alkenes and gem-difluoroalkenes by H⁻

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(5), С. 1388 - 1394

Опубликована: Янв. 1, 2024

Zn-catalyzed stereoselective hydrodefluorination of CF 3 -substituted alkenes, gem -difluoroalkenes and polyfluoroarenes by hydride ion addition has been realized through controlled C(sp )–F and/or 2 bonds cleavage.

Язык: Английский

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Photochemical and Electrochemical Strategies for Hydrodefluorination of Fluorinated Organic Compounds

Chemistry - A European Journal, Год журнала: 2022, Номер 28(29)

Опубликована: Март 18, 2022

Hydrodefluorination (HDF) is a very important fundamental transformation for conversion of the C-F bond into C-H in organic synthesis. In past decade, much progress has been achieved with HDF through utility low-valent metals, transition-metal complexes and main-group Lewis acids. Recently, novel methods have introduced this purpose photo- electrochemical pathways, which are great significance, due to their considerable environmental economical advantages. This Review highlights fluorinated compounds (FOCs) strategies, along mechanistic insights.

Язык: Английский

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Iron-Catalyzed Allylic Defluorinative Ketone Olefin Coupling

Organic Letters, Год журнала: 2022, Номер 24(17), С. 3211 - 3216

Опубликована: Апрель 28, 2022

In this protocol, we demonstrate our discovery that iron is able to efficiently catalyze the reductive allylic defluorinative ketyl olefin coupling reaction between α-trifluoromethyl alkenes and unactivated ketones. This operationally simple cross-electrophile circumvents use of pre-generated organometallics allows for synthesis diverse functional-group-rich tertiary gem-difluorohomoallylic alcohols through a polarity-reversed strategy. Preliminary mechanistic studies support mechanism proceeds formation/olefin insertion/β-fluoro elimination sequence.

Язык: Английский

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Nickel-Catalyzed Cross-Electrophile Ring Opening/gem-Difluoroallylation of Aziridines

Organic Letters, Год журнала: 2023, Номер 25(31), С. 5756 - 5761

Опубликована: Июль 28, 2023

Herein we report a nickel-catalyzed regioselective cross-electrophile ring opening reaction of sulfonyl-protected aziridines with trifluoromethyl-substituted alkenes as the gem-difluoroallylating agents, providing new and efficient entry to prepare gem-difluorobishomoallylic sulfonamides. Moreover, scaffold 6-fluoro-1,2,3,4-tetrahydropyridine can be constructed starting from products via NaH-mediated intramolecular defluorinative nucleophilic vinylic substitution.

Язык: Английский

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Defluorinative Alkylboration of Alkenes Enabled by Dual Photoredox and Copper Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(5)

Опубликована: Дек. 9, 2023

Abstract A regioselectivity reversed three‐component defluorinative alkylboration of alkenes with trifluoromethyls and bis(pinacolato)diboron via dual photoredox/copper catalysis is reported. The mild conditions are compatible a wide array nonactivated trifluoromethyl aromatics bearing electron‐donating or electron‐neutral substituents, trifluoroacetamides, various terminal internal alkenes, enabling straightforward access to synthetically valuable γ ‐ gem ‐difluoroalkyl boronates high efficiency. Furthermore, this protocol applicable alkene‐tethered furnish ‐difluoromethylene‐containing cyclic compounds. Synthetic applications preliminary mechanistic studies also presented.

Язык: Английский

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Catalyst-free defluorinative alkylation of trifluoromethyls

Green Chemistry, Год журнала: 2023, Номер 25(20), С. 8280 - 8285

Опубликована: Янв. 1, 2023

A visible-light induced catalyst-free strategy was developed for the defluorinative alkylation of trifluoromethyls via CO 2 ˙ − . Various trifluoromethyl derivatives and alkenes could participate in reaction smoothly.

Язык: Английский

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Organo-Photoredox Catalyzed gem-Difluoroallylation of Glycine and Glycine Residue in Peptides

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(6), С. 4056 - 4066

Опубликована: Март 7, 2024

An organo-photoredox catalyzed gem-difluoroallylation of glycine with α-trifluoromethyl alkenes via direct C(sp3)–H functionalization and C–F bond activation has been described. As a consequence, broad range gem-difluoroalkene-containing unnatural amino acids are afforded in moderate to excellent yields. This reaction exhibits multiple merits such as readily available starting materials, substrate scope, mild conditions. The feasibility this highlighted by the late-stage modification several peptides well improved vitro antifungal activity compound 3v toward Valsa mali compared that commercial azoxystrobin.

Язык: Английский

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Recent advances in C–F bond activation of trifluoromethylated carbonyl compounds and derivatives

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(27), С. 5365 - 5376

Опубликована: Янв. 1, 2022

The selective functionalization of inert C–F bonds in trifluoromethylated carbonyl compounds has been summarized and the reaction mechanisms are also discussed.

Язык: Английский

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