Copper-Mediated Radical Fluorine-Atom Transfer to Sulfonyl Radical: A Dramatic 4-Methoxypyridine 1-Oxide Ligand Effect DOI
Hongwei Zhang, Xiaoxiao Sun,

Cheng Ma

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3115 - 3127

Published: Feb. 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.

Language: Английский

One‐dimensional and two‐dimensional synergized nanostructures for high‐performing energy storage and conversion DOI Creative Commons
Xin Li, John Wang

InfoMat, Journal Year: 2019, Volume and Issue: 2(1), P. 3 - 32

Published: Nov. 12, 2019

Abstract To address the worldwide energy challenges, advanced storage and conversion systems with high comprehensive performances, as promising technologies, are inevitably required on a timely basis. The performance of these is intimately dependent properties their electrodes. In addition to electrode materials selection compositional optimization, fabrication designed nanostructure also provides significant benefits for performances. past decade, considerable efforts have been made promote search multidimensional nanostructures containing both one‐dimensional (1D) two‐dimensional (2D) in synergy, namely, 1D‐2D synergized nanostructures. By developing freestanding electrodes such unique nanoarchitectures, structural features electroactivities each component can be manifested, where synergistic among them simultaneously obtained further enhanced properties, increased number active sites, fast electronic/ionic transport, so forth. This review overviews state‐of‐the‐art nanostructures, which broadly divided into three groups, core/shell, cactus‐like, sandwich‐like For category, we introduce from aspects features, methodologies successful applications different types storage/conversion devices, including rechargeable batteries, supercapacitors, water splitting, Finally, main challenges faced by perspectives discussed. image

Language: Английский

Citations

269
Sulfonyl fluorides as targets and substrates in the development of new synthetic methods DOI
Terry Shing‐Bong Lou, Michael C. Willis

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(2), P. 146 - 162

Published: Jan. 19, 2022

Language: Английский

Citations

192
Synthesis of sulfonamide and their synthetic and therapeutic applications: Recent advances DOI
Shovan Mondal,

Suniti Malakar

Tetrahedron, Journal Year: 2020, Volume and Issue: 76(48), P. 131662 - 131662

Published: Oct. 10, 2020

Language: Английский

Citations

143
The Emerging Applications of Sulfur(VI) Fluorides in Catalysis DOI Creative Commons
Cayo Lee,

Alina J. Cook,

Jonathan E. Elisabeth

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(11), P. 6578 - 6589

Published: May 19, 2021

The past decade has witnessed remarkable growth of catalytic transformations in organic sulfur(VI) fluoride chemistry. This Perspective concentrates exclusively on foundational examples that utilize strategies to synthesize and react S(VI) fluorides. Key mechanistic studies aim provide insight toward future systems are emphasized.

Language: Английский

Citations

122
EnT-Mediated N–S Bond Homolysis of a Bifunctional Reagent Leading to Aliphatic Sulfonyl Fluorides DOI
Johannes E. Erchinger,

Reece Hoogesteger,

Ranjini Laskar

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(4), P. 2364 - 2374

Published: Jan. 18, 2023

Sulfur(VI) fluoride exchange (SuFEx) gives rise to a plethora of high-valent sulfur linkages; however, the availability (aliphatic) sulfonyl manifolds lag behind, owing limited sources introducing SO2F moiety via classical two-electron approach. Recently, radical-based methodologies have emerged as complementary strategy increase diversity accessible click partners. In this work, synthesis bench-stable sulfamoyl reagent is presented, which may undergo sigma-bond homolysis upon visible-light-induced sensitization form protected β-amino fluorides from alkene feedstocks. Notably, offers an appealing access various building blocks for peptido fluorides, relevant in medicinal chemistry context, well intriguing entry β-ammonium sulfonates and β-sultams, alkenes. Densely functionalized 1,3-sultones were obtained by employing allyl alcohols substrates. Surprisingly, chloride-derived β-imino underwent S-O bond formation ring closure yield rigid cyclopropyl sulfonate ester under SuFEx conditions. Furthermore, engaging thiol-based hydrogen atom donor reaction, reactivity same can be tuned toward direct aliphatic fluorides. Mechanistic experiments indicate energy transfer (EnT)-mediated process. The transient radical adds product occurs either radical-radical coupling or (HAT), respectively.

Language: Английский

Citations

93
Sulfur(vi) fluorides as tools in biomolecular and medicinal chemistry DOI Creative Commons
Sabrina N. Carneiro, Samuel R. Khasnavis, Jisun Lee

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(7), P. 1356 - 1372

Published: Jan. 1, 2023

This review highlights key advances in the synthesis and biomolecular applications of sulfur( vi )-fluorides.

Language: Английский

Citations

50
Selective Fluorosulfonylation of Thianthrenium Salts Enabled by Electrochemistry DOI
Xianqiang Kong, Yiyi Chen, Qianwen Liu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(4), P. 581 - 586

Published: Jan. 25, 2023

A practical electrochemically driven method for fluorosulfonylation of both aryl and alkyl thianthrenium salts has been disclosed. The strategy does not need external redox reagents or metal catalysts. In combination with C-H thianthrenation aromatics, this provides a new tool the site-selective drugs.

Language: Английский

Citations

45
The same oxygenation-state introduction of hypervalent sulfur under transition-metal-free conditions DOI Open Access

Daming Zeng,

Ming Wang, Wei‐Ping Deng

et al.

Organic Chemistry Frontiers, Journal Year: 2020, Volume and Issue: 7(23), P. 3956 - 3966

Published: Jan. 1, 2020

This review discusses the application of same oxygenation-state introduction hypervalent sulfur strategy under transition-metal-free conditions.

Language: Английский

Citations

123
Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances DOI
Oleksandr O. Grygorenko, Dmitriy M. Volochnyuk, Bohdan V. Vashchenko

et al.

European Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 2021(47), P. 6478 - 6510

Published: Sept. 8, 2021

Abstract Current medicinal chemistry relies heavily on the quality of building blocks, i. e. reagents used to introduce chemical diversity into target molecules. The last decade witnessed an emergence many novel (or well‐overlooked old) chemotypes for drug discovery, which is related adapting new synthetic methodologies, designing sp 3 ‐enriched bioisosteres, paying attention previously underrated even unwanted) structural motifs, or combination thereof. In this review with 532 references, a survey selected that emerged recently in provided, focus synthesis corresponding blocks. Thus, saturated (hetero)aliphatic boronates, sulfonyl fluorides, sulfinates, non‐classical benzene isosteres, bicyclic morpholine/piperidine/piperazine analogs, as well gem ‐difluorinated cycloalkanes (as example emerging fluorinated motifs) are discussed.

Language: Английский

Citations

95
Radical Fluorosulfonylation: Accessing Alkenyl Sulfonyl Fluorides from Alkenes DOI
Xingliang Nie, Tianxiao Xu, Jinshuai Song

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(8), P. 3956 - 3960

Published: Nov. 16, 2020

Sulfonyl fluorides have widespread applications in many fields. In particular, their unique biological activity has drawn considerable research interest the context of chemical biology and drug discovery past years. Therefore, new efficient methods for synthesis sulfonyl are highly demand. contrast to extensive studies on FSO2+ -type reagents, a radical fluorosulfonylation reaction with fluorosulfonyl (FSO2. ) remains elusive so far, probably owing its instability difficulty generation. Herein, development first alkenes based FSO2 radicals generated under photoredox conditions is reported. This approach provides general access alkenyl fluorides, including structures that would otherwise be challenging synthesize previously established cross-coupling methods. Moreover, extension late-stage natural products also demonstrated.

Language: Английский

Citations

88