Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Language: Английский

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Divergent C(sp²)–H arylation of heterocycles via organic photoredox catalysis

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(7), P. 3017 - 3022

Published: Jan. 1, 2022

Introducing aryl moieties into heterocyclic scaffolds is a key step in the syntheses of natural products, drugs, and functional materials.

Language: Английский

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Recent progress in the application of iodonium ylides in organic synthesis

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(24), P. 6999 - 7015

Published: Jan. 1, 2022

This review summarizes the recent advances in synthetic application of iodonium ylides covering 2017 to 2022.

Language: Английский

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Condition-Controlled Selective Synthesis of Pyranone-Tethered Indazoles or Carbazoles through the Cascade Reactions of N-Nitrosoanilines with Iodonium Ylides

Organic Letters, Journal Year: 2023, Volume and Issue: 25(24), P. 4422 - 4428

Published: June 8, 2023

Presented herein is a condition-controlled selective synthesis of pyranone-tethered indazoles or carbazole derivatives via the cascade reactions N-nitrosoanilines with iodonium ylides. Mechanistically, formation former involves an unprecedented process including nitroso group-directed C(sp2)–H bond alkylation N-nitrosoaniline ylide followed by intramolecular C-nucleophilic addition to moiety, solvent-assisted cyclohexanedione ring opening, and transesterification/annulation. On contrary, latter initial annulation denitrosation. These developed protocols feature easily controllable selectivity, mild reaction conditions, clean sustainable oxidant (air), valuable products that are structurally diverse. In addition, utility was showcased their facile diverse transformations into synthetically biologically interesting compounds.

Language: Английский

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Rh(iii)-catalyzed C–H annulation of sulfoxonium ylides with iodonium ylides towards isocoumarins

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(5), P. 1112 - 1116

Published: Jan. 1, 2022

The direct synthesis of isocoumarin skeletons has been realized through the Rh( iii )-catalyzed [3 + 3] annulation sulfoxonium ylides and iodonium under mild conditions.

Language: Английский

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Ru(II)-Catalyzed Decarbonylative Alkylation and Annulations of Benzaldehydes with Iodonium Ylides under Chelation Assistance

Organic Letters, Journal Year: 2022, Volume and Issue: 24(29), P. 5281 - 5286

Published: July 18, 2022

A Ru(II)-catalyzed decarbonylative alkylation and annulation of salicylaldehydes 2-aminobenzaldehydes with iodonium ylides has been developed for the synthesis dibenzo[b,d]furans NH-free carbazolones. The reaction proceeds smoothly under mild conditions a low catalyst loading broad substrate compatibility. Notably, hydroxy free amino groups were demonstrated to be effective directing groups, enabling successful aldehyde C–H bond activation subsequent decarbonylation inexpensive Ru(II) catalyst.

Language: Английский

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Rhodium(III)‐Catalyzed Divergent C−H Functionalization of N‐Aryl Amidines with Iodonium Ylides: Access to Carbazolones and Zwitterionic Salts

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(11), P. 1817 - 1823

Published: Feb. 7, 2023

Abstract We described an Rhodium(III)‐catalyzed divergent C−H bond functionalization of N ‐aryl amidines with iodonium ylides. Carbazolones and zwitterionic salts were diversely constructed through intermolecular annulation intramolecular proton transfer under the different reaction conditions. This protocol is operationally simple tolerates a variety functional groups. The efficient post‐modification pharmaceutical molecules demonstrates its practicability.

Language: Английский

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Rh-Catalyzed C–H Activation/Annulation of Enaminones and Cyclic 1,3-Dicarbonyl Compounds: An Access to Isocoumarins

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(9), P. 5348 - 5358

Published: April 3, 2023

A facile access to isocoumarins has been established via rhodium(III)-catalyzed C-H bond activation and intramolecular C-C cascade annulation of enaminones cyclic 1,3-dicarbonyl compounds. The synthetic protocol features a wide range substrates with high functional group tolerance, mild reaction conditions, the selective cleavage enaminone bond. Notably, compounds can in situ-generate iodonium ylide as carbene precursor prepare polycyclic scaffolds by reacting PhI(OAc)2. application this method useful precursors bioactive skeletons is also exemplified.

Language: Английский

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Accessing 7,8-Dihydroquinoline-2,5-diones via Rh-Catalyzed Olefinic C–H Activation/[4+2] Cyclization

Organic Letters, Journal Year: 2024, Volume and Issue: 26(24), P. 5136 - 5140

Published: June 7, 2024

Herein, we report a rhodium-catalyzed C–H activation/[4+2] cyclization reaction between α,β-unsaturated amides and iodonium ylides for the synthesis of novel 7,8-dihydroquinoline-2,5-diones analogues. This protocol provides series pyridones fused with saturated cycles good functional group compatibility, water air tolerance, to excellent yields under mild green conditions. Additionally, scale-up can be smoothly performed as low 0.25 mol % catalyst loading. Recycling experiments different transformation were also carried out demonstrate potential synthetic utility this protocol.

Language: Английский

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Iodonium ylides: an emerging and alternative carbene precursor for C–H functionalizations

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 21(1), P. 24 - 38

Published: Nov. 23, 2022

The metal-catalyzed successive activation and functionalization of arene/heteroarene is one the most fundamental transformations in organic synthesis leads to privileged scaffolds natural products, pharmaceuticals, agrochemicals, fine chemicals. Particularly, transition-metal-catalyzed C-H arenes with carbene precursors via metal migratory insertion has been well studied. As a result, diverse have evaluated, such as diazo compounds, sulfoxonium ylides, triazoles, etc. In addition, there significant developments use iodonium ylides recent years, these reactions proceed high efficiencies selectivities. This review provides comprehensive overview functionalizations, including scope, limitations, their potential synthetic applications.

Language: Английский

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