Iridium Photoredox-Catalyzed Stereoselective C-Glycosylation with Tetrafluoropyridin-4-yl Thioglycosides: A Facile Synthesis of C-α/β-Glucogallins and Their Antioxidant Activity

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17727 - 17738

Published: Nov. 18, 2024

We demonstrate an efficient, scalable, and stereoselective C-glycosylation with thioglycosides possessing a unique photoactive tetrafluoropyridin-4-yl (TFPy) thio radical leaving group, affording editable medicinally biologically essential C-α-glucogallin derivatives. In the presence of silyl enol ether acceptors, desulfurative coupling reaction performs smoothly under mild conditions upon exposure to blue light irradiation. This versatile protocol permits synthesis sugar-drug chimeras by C1 ketonylation complex drug-derived ethers. The scale-up synthesis, anomeric epimerization, post-C-glycosylation modification ketone sugars showcase reaction's potential utilities. Furthermore, could be applied direct carbohydrate skeleton editing equipping group on nonanomeric position. is viable for unprotected TFPy thioglycoside, route ketonyl sugars. concise six-step assembly both configurated C-glucogallins from commercially cheap glucose pentaacetate their antioxidant reactivity investigations underline promising medicinal relevance our current protocols. mechanism was investigated through trapping experiment, oxocarbenium fluorescence quenching Stern–Volmer analysis, confirming that major glycosyl intermediates are generated thioglycoside donors, whose effectively quench excited Ir(ppy)3 oxidative process, complementary product, accounting examples moderate selectivities.

Language: Английский

---

FluoroFusion: NHC-Catalyzed Nucleophilic Aromatic Substitution Reaction Unveils Functional Perfluorinated Diarylmethanones

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2338 - 2342

Published: March 8, 2024

A mild, facile, and metal-free approach via the N-heterocyclic carbene-catalyzed SNAr reaction between aryl aldehydes with perfluoroarenes to obtain coveted functional perfluorinated diarylmethanones is disclosed. This method accommodates a diverse substrate range exhibits notable tolerance toward various groups. Our success in modifying biologically relevant molecules, crafting fully fluorinated bioisosteric analogue of drug candidate D1, highlighting potential these ketones as valuable electrolyte additives for lithium-ion batteries (LIBs) underscores versatility our methodology.

Language: Английский

---

Synthesis of Substituted N'‐(3,5,6,7,8‐Pentafluoro‐1,4‐Dioxo‐1,4‐Dihydronaphthalen‐2‐yl)Hydrazides by Condensation of Acyl Hydrazines and Perfluoro‐1,4‐Naphthoquinone

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(43)

Published: Nov. 1, 2024

Abstract The reaction of different acyl hydrazines with hexafluoro‐1,4‐napthoquinone was studied for the first time. It demonstrated that this interaction stops at substitution one fluorine atom in quinone moiety. Based on observed reaction, a general approach to synthesis pentafluoro‐1,4‐dioxo‐1,4‐dihydronaphthalen‐2‐yl hydrazides developed. revealed optimal conditions condensation are reflux MeOH 0.25 h; note, protocol does not require any chromatographic purification target products. method is versatile and makes it possible prepare products containing various substituents aryl part molecule. In addition, alkyl heteroaryl can be employed as starting compounds too, presence hydroxy cyano groups applied interfere condensation. structure obtained products, namely 4‐chloro‐N□‐(3,5,6,7,8‐pentafluoro‐1,4‐dioxo‐1,4‐dihydronaphthalen‐2‐yl)benzohydrazide, confirmed by X‐ray diffraction. crystals hydrazide, both NH form intermolecular hydrogen bonds give rise layers lying [001] plane. Prepared N'‐(3,5,6,7,8‐pentafluoro‐1,4‐dioxo‐1,4‐dihydronaphthalen‐2‐yl)hydrazides interest redox‐active ligands precursors obtaining wide range functionalized 1,4‐napthoquinones medicine chemistry.

Language: Английский

---

Ketone-Derived Pro-aromatic Reagents for Radical Group Transfer Reactions and Deconstructive Functionalizations

Synlett, Journal Year: 2023, Volume and Issue: 35(10), P. 1072 - 1088

Published: Oct. 24, 2023

Abstract The recent prominence of ketones as handles for sp3-rich radicals has expanded the paradigm synthetic utility ketones, putting ubiquitous functional group once again into spotlight in years. One emerging strategy arose through ketone-derived pro-aromatic reagents form dihydrobenzothiazoline (BTZ), dihydroquinazolinone (DHQZ), dihydropyrazole (DHP), and dihydro-1,2,4-triazole (DHT) key intermediates aromaticity-promoted C–C bond homolytic fission. formed sp3-radicals could then participate various radical functionalizations, including alkylations, arylations, olefination, alkynylation, silylations, amination, thiolation, deuteration, among others, either photocatalytic, thermal, or oxidative conditions. In this review, we highlight implications advances using these transfer reactions deconstructive functionalization. 1 Introduction 2 Aromatization-Driven Bond Scission Ketones 3 Photochemical Reactions Ketone-Derived Pro-aromatic Reagents 4 Non-photochemical 5 Conclusion Future Outlook

Language: Английский

---

Site-selective nucleophilic substitution reactions of pentafluoropyridine with hydroxybenzaldehydes: synthesis of triarylmethanes comprising perfluoropyridine moieties

New Journal of Chemistry, Journal Year: 2023, Volume and Issue: 47(22), P. 10645 - 10658

Published: Jan. 1, 2023

The site-selective nucleophilic attacks of hydroxybenzaldehydes on PFP were used to prepare several perfluoropyridinated (oxy)benzaldehydes. F-C alkylation reaction arenes/heteroarenes with the derived products under SSA catalysis afforded novel fluorinated TRAMs.

Language: Английский

---

Halogenated Phenylpyridines Possessing Chemo-Selectivity for Diverse Molecular Architectures

ACS Omega, Journal Year: 2024, Volume and Issue: 9(26), P. 28961 - 28968

Published: June 18, 2024

Pentafluoropyridine was used as a molecular building block for the installation of aryl bromides, affording series multisubstituted halogenated arenes. This operationally simplistic methodology offers precise regioselectivity, ease scalability, and high purity.

Language: Английский

---

A protocol for the gram-scale synthesis of polyfluoroaryl sulfides via an S Ar step

STAR Protocols, Journal Year: 2023, Volume and Issue: 4(1), P. 102043 - 102043

Published: Jan. 20, 2023

Polyfluoroaryl sulfide is one of the prevalent motifs ubiquitous in materials and pharmaceutical chemistry. We herein describe a simple yet efficient procedure for their synthesis from readily available thiols polyfluoroarenes via an SNAr step. detail specific steps gram-scale preparation 2-((perfluoropyridin-4-yl)thio)benzo[d]thiazole 3 mercaptobenzothiazole 1 pentafluoropyridine 2. For complete details on use execution this protocol, please refer to Liao et al. (2022).1.

Language: Английский

---

Utilizing perhalopyridine-based alkynes as suitable precursors for the synthesis of novel poly(1,2,3-triazolyl)-substituted perhalopyridines

RSC Advances, Journal Year: 2024, Volume and Issue: 14(42), P. 30873 - 30885

Published: Jan. 1, 2024

A novel series of poly(1,2,3-triazolyl)-substituted perhalopyridines were synthesized under ultrasonic irradiation. We also developed an effective method for the preparation ((1,2,3-triazol-4-yl)methoxy)-3,4,5,6-tetrachloropyridines.

Language: Английский

---

Mechanochemical β‐Halogenation of nickel(II) porphyrins at room temperature

Journal of the Chinese Chemical Society, Journal Year: 2023, Volume and Issue: 70(5), P. 1116 - 1124

Published: March 29, 2023

Abstract A room temperature and solvent‐free β ‐chlorination ‐bromination protocol for meso ‐tetraarylporphyrinato nickel(II) complexes to access the ‐octahalogenated derivatives by ball‐milling is communicated. Various parameters were systematically studied.

Language: Английский

---