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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Nickel-Catalyzed Enantioselective Electrochemical Reductive Cross-Coupling of Aryl Aziridines with Alkenyl Bromides

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6270 - 6279

Published: March 7, 2023

An electrochemically driven nickel-catalyzed enantioselective reductive cross-coupling of aryl aziridines with alkenyl bromides has been developed, affording enantioenriched β-aryl homoallylic amines excellent E-selectivity. This electroreductive strategy proceeds in the absence heterogeneous metal reductants and sacrificial anodes by employing constant current electrolysis an undivided cell triethylamine as a terminal reductant. The reaction features mild conditions, remarkable stereocontrol, broad substrate scope, functional group compatibility, which was illustrated late-stage functionalization bioactive molecules. Mechanistic studies indicate that this transformation conforms stereoconvergent mechanism aziridine is activated through nucleophilic halide ring-opening process.

Language: Английский

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Electroreductive Cross‐Electrophile Coupling (eXEC) Reactions

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: June 16, 2023

Abstract Electrochemistry utilizes electrons as a potent, controllable, and traceless alternative to chemical oxidants or reductants, typically offers more sustainable option for achieving selective organic synthesis. Recently, the merger of electrochemistry with readily available electrophiles has been recognized viable increasingly popular methodology efficiently constructing challenging C−C C‐heteroatom bonds in manner complex molecules. In this mini‐review, we have systematically summarized most recent advances electroreductive cross‐electrophile coupling (eXEC) reactions during last decade. Our focus on electrophiles, including aryl alkyl (pseudo)halides, well small molecules such CO 2 , SO D O.

Language: Английский

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A guide to organic electroreduction using sacrificial anodes

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(4), P. 1168 - 1188

Published: Jan. 1, 2023

This review focuses on recent advances in sacrificial anode-enabled organic electroreductions.

Language: Английский

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Interrogating the Mechanistic Features of Ni(I)-Mediated Aryl Iodide Oxidative Addition Using Electroanalytical and Statistical Modeling Techniques

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8689 - 8699

Published: April 4, 2023

While the oxidative addition of Ni(I) to aryl iodides has been commonly proposed in catalytic methods, an in-depth mechanistic understanding this fundamental process is still lacking. Herein, we describe a detailed study using electroanalytical and statistical modeling techniques. Electroanalytical techniques allowed rapid measurement rates for diverse set iodide substrates four classes catalytically relevant complexes (Ni(MeBPy), Ni(MePhen), Ni(Terpy), Ni(BPP)). With >200 experimental rate measurements, were able identify essential electronic steric factors impacting through multivariate linear regression models. This led classification mechanisms, either three-center concerted or halogen-atom abstraction pathway based on ligand type. A global heat map predicted was created shown applicable better reaction outcome case Ni-catalyzed coupling reaction.

Language: Английский

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Overview of Recent Scale-Ups in Organic Electrosynthesis (2000–2023)

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(2), P. 338 - 366

Published: Jan. 18, 2024

This review summarizes examples of organic electrosynthesis from the peer-reviewed literature 2000 to 2023 that have been conducted on scales 20 g or above. A significant portion these were a ≤100 scale, while detailed reports kilogram-scale remain scarce in pharmaceutical industry. In addition chemical transformation, this also highlights type reactor used and projected productivity metric as ways compare different reports. The selected scale-ups described herein illustrate remaining challenges currently preventing routine use large-scale

Language: Английский

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Direct electrochemical synthesis of arenesulfonyl fluorides from nitroarenes: a dramatic ionic liquid effect

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(6), P. 3435 - 3440

Published: Jan. 1, 2024

A practical electrosynthesis of aryl sulfonyl fluorides from nitroarenes is described. Cheap N -methylimidazolium p -toluenesulfonate has been found to be an effective additive, promoting the desired fluorosulfonylation under very mild conditions.

Language: Английский

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Scalable, Chemoselective Nickel Electrocatalytic Sulfinylation of Aryl Halides with SO₂

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(37)

Published: July 12, 2022

Abstract Simple access to aryl sulfinates from iodides and bromides is reported using an inexpensive Ni‐electrocatalytic protocol. The reaction exhibits a broad scope, uses stock solution of simple SO 2 as sulfur source, can be scaled up in batch recycle flow settings. limitations this are clearly shown put into context by benchmarking with state‐of‐the‐art Pd‐based methods.

Language: Английский

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One-Pot Synthesis of Sulfonamides from Unactivated Acids and Amines via Aromatic Decarboxylative Halosulfonylation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21189 - 21196

Published: Sept. 20, 2023

The coupling of carboxylic acids and amines to form amide linkages is the most commonly performed reaction in pharmaceutical industry. Herein, we report a new strategy that merges these traditional partners generate sulfonamides, important bioisosteres. This method leverages copper ligand-to-metal charge transfer (LMCT) convert aromatic sulfonyl chlorides, followed by one-pot amination corresponding sulfonamide. process requires no prefunctionalization native acid or amine extends diverse set aryl, heteroaryl, s-rich aliphatic substrates. Further, extend this synthesis (hetero)aryl fluorides, which have found utility as "click" handles chemical probes programmable bifunctional reagents. Finally, demonstrate protocols analogue synthesis.

Language: Английский

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Nickel‐Catalyzed Sulfonylation of Aryl Bromides Enabled by Potassium Metabisulfite as a Uniquely Effective SO₂ Surrogate

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(19)

Published: March 10, 2023

The development and mechanistic investigation of a nickel-catalyzed sulfonylation aryl bromides is disclosed. reaction proceeds in good yields for variety substrates utilizes an inexpensive, stench-free, inorganic sulfur salt (K2 S2 O5 ) as uniquely effective SO2 surrogate. active oxidative addition complex was synthesized, isolated, fully characterized by combination NMR spectroscopy X-ray crystallography analysis. use the isolated both stoichiometric catalytic reactions revealed that insertion occurs via dissolved , likely released upon thermal decomposition K2 . Key to success role reservoir slowly released, thus preventing catalyst poisoning.

Language: Английский

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