Photoredox Catalysis-Enabled Sulfination of Alcohols and Bromides

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(38), P. 20767 - 20774

Published: Sept. 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.

Language: Английский

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Decarboxylative Sulfonylation of Carboxylic Acids under Mild Photomediated Iron Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(12), P. 2381 - 2386

Published: March 15, 2024

Organic sulfones are an important class of chemical compounds widely used in many research fields. The direct decarboxylative sulfonylation carboxylic acids is attractive but challenging, particularly when iron as a metal catalyst. Herein, we describe photoinduced iron-catalytic method for the synthesis directly using via radical-based decarboxylation. This protocol mild, highly efficient, and easy-to-operate. A broad scope carbon electrophiles could be well tolerated. mechanism involving iron-catalyzed decarboxylation, radical transfer, single-electron reduction, nucleophilic attack proposed.

Language: Английский

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Multimodal Acridine Photocatalysis Enables Direct Access to Thiols from Carboxylic Acids and Elemental Sulfur

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6973 - 6980

Published: April 19, 2024

Development of photocatalytic systems that facilitate mechanistically divergent steps in complex catalytic manifolds by distinct activation modes can enable previously inaccessible synthetic transformations. However, multimodal remain understudied, impeding their implementation methodology. We report herein a access to thiols directly merges the structural diversity carboxylic acids with ready availability elemental sulfur without substrate preactivation. The transformation provides direct radical-mediated segue one most biologically important and synthetically versatile organosulfur functionalities, whose accessibility remains largely dominated two-electron-mediated processes based on toxic uneconomical reagents precursors. two-phase radical process is facilitated reactivity acridine photocatalysis enables both singlet excited state PCET-mediated decarboxylative carbon–sulfur bond formation unknown reductive disulfur cleavage photoinduced hydrogen atom transfer silane–triplet system. study points significant potential providing unexplored directions

Language: Английский

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Sulfonylation from sodium dithionite or thiourea dioxide

Chinese Chemical Letters, Journal Year: 2020, Volume and Issue: 32(1), P. 461 - 464

Published: May 12, 2020

Language: Английский

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Metal-free C(sp2)-H perfluoroalkylsulfonylation and configuration inversion: Stereoselective synthesis of α-perfluoroalkylsulfonyl E-enaminones

Chinese Chemical Letters, Journal Year: 2021, Volume and Issue: 32(11), P. 3514 - 3517

Published: April 28, 2021

Language: Английский

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