Decatungstate-Catalyzed C(sp³)–H Sulfinylation: Rapid Access to Diverse Organosulfur Functionality

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(26), С. 9737 - 9743

Опубликована: Июнь 23, 2021

Here we report the direct conversion of strong, aliphatic C(

Язык: Английский

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Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(16)

Опубликована: Янв. 29, 2024

Abstract We highlight key contributions in the field of direct radical C Ar − H (hetero)aromatic functionalization involving fluorinated radicals. A compilation Functional Group Transfer Reagents and their diverse activation mechanisms leading to release radicals are discussed. The substrate scope for each is analyzed classified into three categories according electronic properties substrates. Density functional theory computational analysis provides insights chemical reactivity several through electrophilicity nucleophilicity parameters. Theoretical reduction potentials also highlights remarkable correlation between oxidizing ability. It established that highly (e.g. ⋅OCF 3 ) capable engaging single‐electron transfer (SET) processes rather than addition, which good agreement with experimental literature data. scale, based on barrier addition these benzene elaborated using high accuracy DLPNO‐(U)CCSD(T) method.

Язык: Английский

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Magnetically recoverable catalysts for efficient multicomponent synthesis of organosulfur compounds

RSC Advances, Год журнала: 2025, Номер 15(5), С. 3928 - 3953

Опубликована: Янв. 1, 2025

This review studies magnetically recoverable catalysts designed for the efficient multicomponent synthesis of organosulfur compounds. These enhance process by combining efficiency with environmental sustainability.

Язык: Английский

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Scalable, Chemoselective Nickel Electrocatalytic Sulfinylation of Aryl Halides with SO₂

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(37)

Опубликована: Июль 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.

Язык: Английский

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Generation and Use of Glycosyl Radicals under Acidic Conditions: Glycosyl Sulfinates as Precursors

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(16)

Опубликована: Фев. 10, 2023

We herein report a method that enables the generation of glycosyl radicals under highly acidic conditions. Key to success is design and use sulfinates as radical precursors, which are bench-stable solids can be readily prepared from commercial starting materials. This development allows installation units onto pyridine rings directly by Minisci reaction. further demonstrate utility this in late-stage modification complex drug molecules, including anticancer agent camptothecin. Experimental studies provide insight into reaction mechanism.

Язык: Английский

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Photoredox Catalysis-Enabled Sulfination of Alcohols and Bromides

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(38), С. 20767 - 20774

Опубликована: Сен. 18, 2023

Sulfinates are important lynchpin intermediates in pharmaceutical production; however, their synthesis via photoredox catalysis is challenging because of facile oxidation. We herein disclose a photocatalytic strategy for the direct conversion alcohols and alkyl bromides into sulfinates. These transformations enabled by utilization easily oxidized radical precursors─namely, alcohol N-heterocyclic carbene adducts N-adamantyl aminosupersilane─that facilitate efficient oxidatively labile sulfinate products. A broad range functional groups amenable to reported transformations, providing rapid access sulfonamides, sulfonyl halides, sulfones, sulfonic acids. The utility these methods further demonstrated late-stage diversification natural products drugs pharmaceutically relevant sulfonamides "clickable" fluorides. In summary, this work illustrates potential novel precursors expand breadth transformations.

Язык: Английский

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Photocatalytic Sulfonylation: Innovations and Applications

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Июль 14, 2024

Photosynthesis, converting sustainable solar energy into chemical energy, has emerged as a promising craft to achieve diverse organic transformations due its mild reaction conditions, sustainability, and high efficiency. The synthesis of sulfonated compounds drawn significant attention in the pharmaceuticals, agrochemicals, materials industries unique structure electronic properties sulfonyl groups. Over past decades, many photocatalytic sulfonylation reactions have been developed. In this review, recent advances photocatalyzed reviewed since 2020, with primary focus on discussing design mechanism.

Язык: Английский

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Mining the Carbon Intermediates in Plastic Waste Upcycling for Constructing C–S Bond

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(27), С. 18639 - 18649

Опубликована: Июнь 25, 2024

Postconsumer plastics are generally perceived as valueless with only a small portion of plastic waste being closed-loop recycled into similar products while most them discarded in landfills. Depositing landfills not harms the environment but also signifies substantial economic loss. Alternatively, constructing value-added chemical feedstocks via mining waste-derived intermediate species carbon (C) source under mild electrochemical conditions is sustainable strategy to realize circular economy. This proof-of-concept work provides an attractive "turning trash treasure" by integrating electrocatalytic polyethylene terephthalate (PET) upcycling C–S coupling reaction synthesize organosulfur compounds, hydroxymethanesulfonate (HMS). HMS can be produced efficiently (Faradaic efficiency, FE ∼70%) deliberately capturing electrophilic intermediates generated PET monomer (ethylene glycol, EG) process, followed nucleophilic sulfur (S) (i.e., SO32– and HSO3–). Unlike many previous studies conducted alkaline conditions, was performed over amorphous MnO2 catalyst near-neutral allowing for stabilization intermediates. The compatibility this further investigated employing biomass-derived compounds substrates. Moreover, comparable yields achieved real-world plastics, showing its enormous potential practical application. Lastly, Density function theory (DFT) calculation reveals that C–C cleavage step EG rate-determining (RDS), significantly decreases energy barriers both RDS when compared crystalline counterpart.

Язык: Английский

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C(sp3)–H sulfinylation of light hydrocarbons with sulfur dioxide via hydrogen atom transfer photocatalysis in flow

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 19, 2024

Abstract Sulfur-containing scaffolds originating from small alkyl fragments play a crucial role in various pharmaceuticals, agrochemicals, and materials. Nonetheless, their synthesis using conventional methods presents significant challenges. In this study, we introduce practical efficient approach that harnesses hydrogen atom transfer photocatalysis to activate volatile alkanes, such as isobutane, butane, propane, ethane, methane. Subsequently, these nucleophilic radicals react with SO 2 yield the corresponding sulfinates. These sulfinates then serve versatile building blocks for of diverse sulfur-containing organic compounds, including sulfones, sulfonamides, sulfonate esters. Our use flow technology offers robust, safe scalable platform effectively activating challenging gaseous facilitating transformation into valuable

Язык: Английский

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A radical Smiles rearrangement difunctionalization of activated alkenes via desulfonylation and insertion of sulfur dioxide relay strategy

Green Chemistry, Год журнала: 2024, Номер 26(11), С. 6774 - 6778

Опубликована: Янв. 1, 2024

A novel and attractive photochemical difunctionalization of N -tosyl acrylamide for constructing alkylsulfonylated oxindoles amides with excellent substrate adaptability via a radical Smiles rearrangement strategy is described.

Язык: Английский

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