RSC Advances, Год журнала: 2024, Номер 14(47), С. 34811 - 34815
Опубликована: Янв. 1, 2024
The σ-complex is formed first, followed by the production of two adduct isomers, and ultimately yielding desired product through an elimination reaction.
Язык: Английский
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
Процитировано
17
European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(23)
Опубликована: Май 25, 2024
Abstract Sulfonyl fluorides have widespread applications in many fields, including organic synthesis, chemical biology, drug discovery and materials science. In particular, the past decade, a number of aliphatic sulfonyl been identified showing various biological activities. These appealing features brought about significant advancement developing synthetic methods to access fluorides. this review, we will discuss recent developments radical approaches for synthesis
Язык: Английский
Процитировано
13
Organic Letters, Год журнала: 2023, Номер 25(38), С. 7051 - 7056
Опубликована: Сен. 20, 2023
In this report, we present a photocatalytic ring-opening fluorosulfonylation of strained cycloalkanols with sulfur dioxide and NFSI under mild conditions for the synthesis carbonyl-containing aliphatic sulfonyl fluorides. The synthetic potential fluoride products has been examined by diverse transformations, including SuFEx reactions Baeyer-Villiger oxidation reactions. Mechanistic studies demonstrate that reaction operates through radical C-C bond cleavage/SO2 insertion/fluorination cascade process.
Язык: Английский
Процитировано
17
Organic Letters, Год журнала: 2024, Номер 26(11), С. 2332 - 2337
Опубликована: Март 13, 2024
A practical synthetic method for the synthesis of vinyl sulfonyl fluorides through copper-promoted direct fluorosulfonylation has been developed. The reaction vinylboronic acids with DABSO and then NFSI is performed under mild conditions. This transformation efficiently affords aryl or alkyl good yields, exclusive E-configuration, broad substrate scope, excellent compatibility, operational simplicity.
Язык: Английский
Процитировано
3
Organic Letters, Год журнала: 2025, Номер unknown
Опубликована: Фев. 6, 2025
This study reported a novel and unprecedented photoredox-catalyzed protocol for direct allylic C–H fluorosulfonylation of alkenes with FABI. mild exhibited excellent compatibility various functional groups, broad substrate scope, promising scalability, enabling convenient access to wide range allyl sulfonyl fluorides exceptional regioselectivity. The synthetic robustness this strategy was further demonstrated by the late-stage functionalization natural products their ligation other drugs via SuFEx chemistry.
Язык: Английский
Процитировано
0
Chemical Reviews, Год журнала: 2025, Номер unknown
Опубликована: Апрель 22, 2025
Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern
Язык: Английский
Процитировано
0
Helvetica Chimica Acta, Год журнала: 2023, Номер 107(1)
Опубликована: Дек. 15, 2023
Abstract The incorporation of nitrogen into small molecules is one the highest‐demanded transformations in modern synthetic chemistry. Alkene difunctionalization and aziridination offer desirable approaches to these amino synthons from feedstock precursors. Although groups can be added alkenes following alkene reaction with an initiation reagent, most approach involves direct addition group alkene, allowing for a range possible secondary functionalization outcomes. many strategies have been accomplished through use transition metals, utility metal‐free still at forefront chemistry, both development demand. This review aims present comprehensive history current state‐of‐the‐art metal‐free, alkenes.
Язык: Английский
Процитировано
8
The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(9), С. 6416 - 6427
Опубликована: Апрель 15, 2024
A novel conversion of 1,5-diynols into sulfonylated benzo[b]fluorenes is reported by a TFA-promoted cascade cyclization with sodium sulfinates under mild conditions. This strategy provides an efficient and practical approach for accessing various sulfonated in moderate to excellent yields metal-free On the basis control experimental results density functional theory calculations, possible transformation mechanism consisting dehydration propargylic alcohols, sulfonylation, allenylation, Schmittel-type proposed. It worth noting that TFA played important role this cyclization, which promoted C–SO2R bond cleavage sulfone intermediate form allenyl sulfones, followed give target product.
Язык: Английский
Процитировано
2
Chinese Journal of Chemistry, Год журнала: 2024, Номер unknown
Опубликована: Дек. 2, 2024
Comprehensive Summary Herein, we report a rare example of three‐component net‐oxidative sulfonylation SO 2 surrogate with an oxidatively activated radical precursor under mild and metal‐ external‐oxidant‐free conditions. The mildness sustainability the reaction are enabled by photoelectrocatalysis, 3‐aza‐1,5‐dienes, organotrifluoroborates 1,4‐diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct (DABSO) undergo sulfonylative cyclization to afford sulfono 4‐pyrrolin‐2‐ones in atom‐economical manner broad substrate scope good functional‐group tolerance. protocol is amenable late‐stage diversification complex molecular architectures as well gram‐scale synthesis. Sunlight could be used light source, conducted all‐solar mode using commercially available photovoltaic panel generate electricity situ . Mechanistic studies reveal that generated (DABCO), which was generally innocent previous reactions, functions electron shuttle between photocatalytic cycle reactants.
Язык: Английский
Процитировано
2
Molecules, Год журнала: 2024, Номер 29(11), С. 2559 - 2559
Опубликована: Май 29, 2024
Radical reactions are powerful in the synthesis of diverse molecular scaffolds bearing functional groups. In previous review articles, we have presented 1,2-difunctionalizations, remote 1,3-, 1,4-, 1,5-, 1,6- and 1,7-difunctionalizations, addition followed by cyclization reactions. Presented this paper is radical second functionalization reaction. The could be realized atom transfer reactions, or transition metal-assisted coupling with neutral molecules, cationic anionic species.
Язык: Английский
Процитировано
1