Photocatalytic C–H Trifluoromethylthiolation by the Decatungstate Anion

Organic Letters, Год журнала: 2021, Номер 23(15), С. 5729 - 5733

Опубликована: Июль 14, 2021

A broadly applicable method for the trifluoromethylthiolation of methylene C(sp3)–H, methine α-oxygen and formyl C(sp2)–H bonds is presented using decatungstate anion as sole catalyst. By adjusting substrate ratio reaction concentration, this was applied to 40 examples in good regioselectivities, including derivatization natural products. Furthermore, SCF3–drug analogues were synthesized by subsequent functionalization SCF3 products, highlighting importance photocatalyzed C–H functionalization.

Язык: Английский

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N-Heterocyclic-Carbene-Catalyzed C–H Acylation via Radical Relay

Organic Letters, Год журнала: 2022, Номер 24(3), С. 944 - 948

Опубликована: Янв. 20, 2022

A method of N-fluorocarboxamide-directed N-heterocyclic-carbene (NHC)-catalyzed benzylic C-H acylation with aldehydes via the hydrogen atom transfer strategy is disclosed. This transformation involves a sequence single-electron transfer, 1,5-hydrogen and radical cross-coupling steps. offers facile access to various highly functionalized ketones exhibits good chemical yields functional group tolerance.

Язык: Английский

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Copper-Mediated Radical Fluorine-Atom Transfer to Sulfonyl Radical: A Dramatic 4-Methoxypyridine 1-Oxide Ligand Effect

ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 3115 - 3127

Опубликована: Фев. 13, 2024

Although the transition metal-catalyzed radical fluorine atom transfer (FAT) strategy has emerged as a powerful tool for construction of C–F bonds, to our knowledge, this approach rarely been applied formation S–F bonds. Here, we report that 4-methoxypyridine 1-oxide can serve an inexpensive and simple yet effective ligand thus promote transformation copper-mediated challengeable FAT sulfonyl radicals, paving way assembly FSO2 group. Based on concept, three Cu(I)-catalyzed protocols involving site-selective intra- intermolecular fluorosulfonylation inert C(sp3)–H bonds 1,2-aminofluorosulfonylation inactivated alkenes have developed, enabling preparation C(sp3)-rich aliphatic fluorides cannot be easily synthesized by known methods. These practical operationally methods result in high functional group tolerance under mild conditions modification bioactive derivatives highly valued molecules. Detailed mechanistic studies indicate unique role facilitating such rare FATs via outer-sphere pathway.

Язык: Английский

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Organoselenium compounds in medicinal chemistry

ChemMedChem, Год журнала: 2024, Номер 19(17)

Опубликована: Май 23, 2024

Abstract The chemical and biological interest in this element the molecules bearing selenium has been exponentially growing over years. Selenium, formerly designated as a toxin, becomes vital trace for life that appears selenocysteine its dimeric form, selenocystine, active sites of selenoproteins, which catalyze wide variety reactions, including detoxification reactive oxygen species modulation redox activities. From point view drug developments, organoselenium drugs are isosteres sulfur‐containing oxygen‐containing with advantage presence atom confers antioxidant properties high lipophilicity, would increase cell membrane permeation leading to better oral bioavailability. This statement is paramount relevance considering big number clinically employed compounds sulfur or atoms their structures nucleosides carbohydrates. Thus, article we have focused on relevant features application medicinal chemistry. With increasing chemistry, attempted highlight most significant published data subject, mainly concentrating analysis last In consequence, recent advances pharmacological discussed.

Язык: Английский

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A general method for site-selective Csp³–S bond formation via cooperative catalysis

Chemical Science, Год журнала: 2019, Номер 11(5), С. 1276 - 1282

Опубликована: Дек. 6, 2019

A copper-catalyzed site-selective thiolation of Csp³–H bonds aliphatic amines was developed. The method features a broad substrate scope and good functional group tolerance.

Язык: Английский

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Aza-heterocycles via copper-catalyzed, remote C–H desaturation of amines

Chem, Год журнала: 2021, Номер 8(1), С. 210 - 224

Опубликована: Ноя. 16, 2021

Язык: Английский

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Recent Advances in the Development of Direct Trifluoromethylselenolation Reagents and Methods

Advanced Synthesis & Catalysis, Год журнала: 2021, Номер 363(7), С. 1835 - 1854

Опубликована: Фев. 25, 2021

Abstract The introduction of trifluoromethylchalcogen group (CF 3 O, CF S and Se) has attracted growing attention in the field modern organofluorine chemistry. Compared with O chemistry, methods for trifluoromethylselenolation are much less developed owing to limited availability Se transfer reagents synthetic methods. introduces promising lipophilicity (Hansch‐Leo parameter=1.29) strong electron‐withdrawing effect (Hammett constants σ m =0.44, p =0.45) which important parameters development new pharmaceutically relevant compounds. Traditionally, compounds were synthesized by nucleophilic trifluoromethylation diselenides selenocyanates, suffered from harsh conditions and/or substrates scope. indirect methods, direct formation C−SeCF constitutes is a more efficient approach. In recent years, enabled incorporation trifluoromethylselenyl directly under mild conditions, specifically transition metal catalysis photoredox catalysis. this review, we will focus on strategies based magnified image

Язык: Английский

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Redox Neutral Radical-Relay Cobalt Catalysis toward C–H Fluorination and Amination

Organic Letters, Год журнала: 2020, Номер 22(9), С. 3601 - 3606

Опубликована: Апрель 20, 2020

A redox neutral radical-relay cobalt-catalyzed intramolecular C–H fluorination of N-fluoroamides featuring the in situ formed cobalt fluorides as latent radical fluorinating agents is reported. Moreover, reactivity such a catalysis could be diverted from to amination by engineering substrates' conformational flexibility. Preliminary mechanistic studies (UV–vis spectroscopy, cyclic voltammetry and DFT calculations, etc.) support reaction proceeding mechanism.

Язык: Английский

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Remote Site‐Selective Radical C(sp³)−H Monodeuteration of Amides using D₂O

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(34), С. 18645 - 18650

Опубликована: Июнь 11, 2021

Site-selective incorporation of deuterium into biologically active compounds is high interest in pharmaceutical industry. We present a mild and environmentally benign metal-free method for the remote selective radical C-H monodeuteration aliphatic bonds various amides with inexpensive heavy water (D2 O) as source. The uses easily installed N-allylsulfonyl moiety an N-radical precursor that generates C-radical via site-selective 1,5- or 1,6-hydrogen atom transfer (HAT). Methyl thioglycolate, readily exchanges its proton D2 O, serves deuteration reagent chain-carrier. highly has been applied to different types unactivated sp3 -C-H also next heteroatoms. potential utility this further demonstrated by natural product derivatives drugs.

Язык: Английский

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Catalyst‐Free Decarbonylative Trifluoromethylthiolation Enabled by Electron Donor‐Acceptor Complex Photoactivation

Advanced Synthesis & Catalysis, Год журнала: 2021, Номер 363(14), С. 3507 - 3520

Опубликована: Май 19, 2021

A catalyst- and additive-free decarbonylative trifluoromethylthiolation of aldehyde feedstocks has been developed. This operationally simple, scalable, open-to-air transformation is driven by the selective photoexcitation electron donor-acceptor (EDA) complexes, stemming from association 1,4-dihydropyridines (donor) with N-(trifluoromethylthio)phthalimide (acceptor), to trigger intermolecular single-electron transfer events under ambient- visible light-promoted conditions. Extension other acceptors enables synthesis thiocyanates thioesters, as well difunctionalization [1.1.1] propellane. The mechanistic intricacies this photochemical paradigm are elucidated through a combination experimental efforts high-level quantum mechanical calculations [dispersion-corrected (U)DFT, DLPNO-CCSD(T), TD-DFT]. comprehensive study highlights necessity for EDA complexation efficient alkyl radical generation. Computation subsequent ground state pathways reveals that SH2 addition intermediate complex extremely exergonic results in charge event dihydropyridine donor acceptor complex. Experimental computational further suggest product formation also occurs via reaction radicals 1,2-bis(trifluoromethyl)disulfane, generated in-situ thiyl radicals.

Язык: Английский

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