Sulfonyl fluorides as targets and substrates in the development of new synthetic methods

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

Published: Jan. 19, 2022

Language: Английский

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The Emerging Applications of Sulfur(VI) Fluorides in Catalysis

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

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EnT-Mediated N–S Bond Homolysis of a Bifunctional Reagent Leading to Aliphatic Sulfonyl Fluorides

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

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Functional group divergence and the structural basis of acridine photocatalysis revealed by direct decarboxysulfonylation

Chemical Science, Journal Year: 2022, Volume and Issue: 13(14), P. 4170 - 4179

Published: Jan. 1, 2022

The reactivity of the sulfonyl group varies dramatically from nucleophilic sulfinates through chemically robust sulfones to electrophilic halides-a feature that has been used extensively in medicinal chemistry, synthesis, and materials science, especially as bioisosteric replacements structural analogs carboxylic acids other carbonyls. Despite great synthetic potential functional interconversions, a method can convert directly sulfones, halides remained out reach. We report herein development photocatalytic system for first time enables direct decarboxylative conversion sulfinates, well chlorides fluorides one step multicomponent fashion. A mechanistic study prompted by new revealed key features acridine photocatalysts facilitate transformations provided an informative predictive multivariate linear regression model quantitatively relates with activity.

Language: Английский

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Advances in the construction of diverse SuFEx linkers

National Science Review, Journal Year: 2023, Volume and Issue: 10(6)

Published: April 29, 2023

Abstract Sulfur fluoride exchange (SuFEx), a new generation of click chemistry, was first presented by Sharpless, Dong and co-workers in 2014. Owing to the high stability yet efficient reactivity SVI–F bond, SuFEx has found widespread applications organic synthesis, materials science, chemical biology drug discovery. A diverse collection linkers emerged, involving gaseous SO2F2 SOF4 hubs; SOF4-derived iminosulfur oxydifluorides; O-, N- C-attached sulfonyl fluorides sulfonimidoyl fluorides; novel sulfondiimidoyl fluorides. This review summarizes progress these connectors, with an emphasis on analysing advantages disadvantages synthetic strategies connectors based concept, it is expected be beneficial researchers rapidly correctly understand this field, thus inspiring further development chemistry.

Language: Английский

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Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF

Science, Journal Year: 2023, Volume and Issue: 381(6655), P. 302 - 306

Published: July 20, 2023

All fluorochemicals—including elemental fluorine and nucleophilic, electrophilic, radical fluorinating reagents—are prepared from hydrogen fluoride (HF). This highly toxic corrosive gas is produced by the reaction of acid-grade fluorspar (>97% CaF 2 ) with sulfuric acid under harsh conditions. The use to produce fluorochemicals via a process that bypasses HF desirable but remains an unsolved problem because prohibitive insolubility . Inspired calcium phosphate biomineralization, we herein disclose protocol treating dipotassium (K HPO 4 mechanochemical affords solid composed crystalline K 3 (HPO )F 2− x Ca y (PO F) b , which found suitable for forging sulfur-fluorine carbon-fluorine bonds.

Language: Английский

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Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

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

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Introducing A New Class of Sulfonyl Fluoride Hubs via Radical Chloro‐Fluorosulfonylation of Alkynes

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(40), P. 22035 - 22042

Published: Aug. 12, 2021

Sulfonyl fluorides have widespread applications in many important fields, including ligation chemistry, chemical biology, and drug discovery. Therefore, new methods to increase the synthetic efficiency expand available structures of sulfonyl are highly demand. Here, we introduce a powerful class fluoride hubs, β-chloro alkenylsulfonyl (BCASF), which can be constructed via radical chloro-fluorosulfonyl difunctionalization alkynes under photoredox conditions. BCASF molecules exhibit versatile reactivities well undergo series transformations at chloride site while keeping group intact, reduction, Suzuki coupling, Sonogashira as nucleophilic substitution with various nitrogen, oxygen, sulfur nucleophiles. By using hub, wide range becomes readily accessible, such cis fluorides, dienylsulfonyl ynenylsulfonyl challenging or even not possible synthesize before known methods. Moreover, further application late-stage modification peptides drugs is also demonstrated.

Language: Английский

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Redox-Neutral Organometallic Elementary Steps at Bismuth: Catalytic Synthesis of Aryl Sulfonyl Fluorides

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(51), P. 21497 - 21502

Published: Dec. 16, 2021

A Bi-catalyzed synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids is presented. We demonstrate that organobismuth(III) catalysts bearing a bis-aryl sulfone ligand backbone revolve through different canonical organometallic steps within catalytic cycle without modifying oxidation state. All have been validated, including insertion SO2 into Bi-C bonds, leading to structurally unique O-bound bismuth sulfinate complex. The protocol affords excellent yields for wide range aryl and heteroaryl acids, displaying functional group tolerance.

Language: Английский

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Recent progress in the synthesis of sulfonyl fluorides for SuFEx click chemistry

Chinese Chemical Letters, Journal Year: 2021, Volume and Issue: 32(9), P. 2736 - 2750

Published: March 18, 2021

Language: Английский

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