General Approach to Amides through Decarboxylative Radical Cross-Coupling of Carboxylic Acids and Isocyanides

Organic Letters, Год журнала: 2024, Номер 26(16), С. 3380 - 3385

Опубликована: Апрель 12, 2024

Herein, we report a silver-catalyzed protocol for decarboxylative cross-coupling between carboxylic acids and isocyanides, leading to linear amide products through free-radical mechanism. The disclosed approach provides general entry variety of decorated amides, accommodating diverse array radical precursors, including aryl, heteroaryl, alkynyl, alkenyl, alkyl acids. Notably, the proved be efficient late-stage functionalization several elaborate pharmaceuticals, demonstrating its potential applications.

Язык: Английский

---

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

---

Electrophotochemical Synthesis Facilitated Trifluoromethylation of Arenes Using Trifluoroacetic Acid

Journal of the American Chemical Society, Год журнала: 2023, Номер unknown

Опубликована: Ноя. 3, 2023

The trifluoromethyl (CF3) group is an essential moiety in medicinal chemistry due to its unique physicochemical properties. While trifluoroacetic acid (TFA) inexpensive and easily accessible reagent, use as a source of CF3 highly challenging high oxidation potential. In this study, we present novel electrophotochemical approach that enables the TFA for selective, catalyst- oxidant-free trifluoromethylation (hetero)arenes. Key our selective over arenes, generating radicals through oxidative decarboxylation. This strategy sustainable environmentally-friendly synthesis CF3-, CF2H- perfluoroalkyl-containing (hetero)arenes with broad range substrates. Importantly, results demonstrate significantly improved chemoselectivity by light irradiation, opening up new possibilities synthetic applications ideal yet underutilized source.

Язык: Английский

---

Stereoretentive Catalytic [3+2]-Cycloaddition/Rearrangement/Decarboxylation Reactions of Indoles with Non-Racemic Donor–Acceptor Cyclopropanes

ACS Catalysis, Год журнала: 2023, Номер 13(3), С. 1621 - 1629

Опубликована: Янв. 12, 2023

A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is reported via a "one-pot" cyclopentannulation-rearrangement cascade reaction that sequentially catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate with 3-methylindole non-racemic donor–acceptor cyclopropanes in high yields enantioretention under mild conditions. Highly diastereoselective [3+2]-cycloaddition dependent on substituents. In addition, further transformation these dihydro-3H-carbazole-2-carboxylates hydrolysis decarboxylation unexpectedly conditions provides straightforward access to the decarboxylated compounds moderate retention enantiomeric purity.

Язык: Английский

---

Catalytic Asymmetric Difluoroalkylation Using In Situ Generated Difluoroenol Species as the Privileged Synthon

Advanced Science, Год журнала: 2024, Номер 11(14)

Опубликована: Фев. 6, 2024

A robust and practical difluoroalkylation synthon, α,α-difluoroenol species, which generated in situ from trifluoromethyl diazo compounds water the presence of dirhodium complex, is disclosed. As compared to presynthesized difluoroenoxysilane formed difluoroenolate under basic conditions, this difluoroenol intermediate displayed versatile reactivity, resulting dramatically improved enantioselectivity mild conditions. demonstrated catalytic asymmetric aldol reaction Mannich reactions with ketones or imines chiral organocatalysts, quinine-derived urea, phosphoric acid (CPA), respectively, relay catalysis strategy provides an effective platform for applying fluorination chemistry. Moreover, method features a novel 1,2-difunctionalization process via installation carbonyl motif alkyl group on two vicinal carbons, complementary protocol metal carbene gem-difunctionalization reaction.

Язык: Английский

---

Access to gem-Difluoroalkenes via Organic Photoredox-Catalyzed gem-Difluoroallylation of Alkyl Iodides

The Journal of Organic Chemistry, Год журнала: 2021, Номер 87(2), С. 1574 - 1584

Опубликована: Дек. 29, 2021

An organic photoredox-catalyzed gem-difluoroallylation of α-trifluoromethyl alkenes with alkyl iodides via C-F bond cleavage for the synthesis gem-difluoroalkene derivatives is reported. This transition-metal-free transformation utilized a readily available dye 4CzIPN as sole photocatalyst and employed common chemical N,N,N',N'-tetramethylethylenediamine radical activator halogen-atom transfer. In addition, variety iodides, including primary, secondary, tertiary were tolerated provided good to high yields.

Язык: Английский

---

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

---

Straightforward Synthesis of Alkyl Fluorides via Visible-Light-Induced Hydromono- and Difluoroalkylations of Alkenes with α-Fluoro Carboxylic Acids

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(14), С. 9232 - 9241

Опубликована: Июнь 24, 2022

We herein report the first visible-light-induced hydromono- and difluoroalkylations of alkenes with inexpensive easily accessible α-fluoro carboxylic acids. This metal-free protocol exhibits mild conditions, high efficiency, excellent functional-group tolerance, providing a straightforward approach to mono- difluoroalkylated alkanes. Moreover, fluorine effect on hydrofluoroalkylation reaction is discussed in detail.

Язык: Английский

---

Electrochemical Decarboxylative Oxygenation of Carboxylic Acids

ACS Sustainable Chemistry & Engineering, Год журнала: 2022, Номер 10(15), С. 5067 - 5071

Опубликована: Апрель 6, 2022

A straightforward electrosynthesis of carbonyls from aliphatic carboxylic acids has been developed through electrochemical decarboxylative oxygenation. This newly transformation features metal free, ubiquitous substrates, good functional group tolerance, and mild conditions. Diverse primary, secondary, as well tertiary were amenable to this sequence, furnishing valuable ketones, aldehydes, amides in excellent yields. Moreover, preliminary mechanistic studies indicate that the electrochemically generated carbocation is trapped with water followed by TEMPO-mediated electrocatalytic oxidation alcohol intermediate.

Язык: Английский

---

Decarboxylative arylation with diaryliodonium(iii) salts: alternative approach for catalyst-free difluoroenolate coupling to aryldifluoromethyl ketones

Green Chemistry, Год журнала: 2023, Номер 25(5), С. 1790 - 1796

Опубликована: Янв. 1, 2023

α-Aryl-α,α-difluoroketones were synthesized via decarboxylative arylation using diaryliodonium salts under catalyst-free conditions without organometallic intermediates. The products can be transformed into various difluorinated functional groups.

Язык: Английский

---