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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Synthesis of 1-Aminoisoquinolines via Rh(III)-Catalyzed C–H Cascade Annulation of Benzamidines with Iodonium Ylides

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

A Rh(III)-catalyzed C-H cascade annulation reaction of benzamidine hydrochlorides with iodonium ylides has been successfully accomplished, providing an efficient strategy for the synthesis various 1-aminoisoquinoline derivatives in moderate to good yields. Here, ylide serves as accessible and safe carbene precursor. Further derivatizations were implemented demonstrate potential utility this reaction. Furthermore, photophysical properties these compounds may have applications photoelectric materials.

Language: Английский

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Iridium(III)-Catalyzed Cyclization of Oximes with Iodonium Ylides: Synthesis of Multisubstituted Heterocyclic N-Oxides

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 29, 2025

Iridium(III)-catalyzed regioselective cyclization of substituted oximes with iodonium ylides has been described. This methodology offered multisubstituted heterocyclic N-oxides under mild reaction conditions in a redox-neutral manner. The was also compatible vinyl oximes. Additionally, substrate diversification carried out to illustrate the synthetic application protocol. A possible mechanism involving C-H bond activation proposed as well supported by isolation key five-membered iridacycle intermediate.

Language: Английский

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Transition-Metal-Catalyzed Directed C–H Bond Functionalization with Iodonium Ylides: A Review of the Last 5 Years

Molecules, Journal Year: 2024, Volume and Issue: 29(15), P. 3567 - 3567

Published: July 29, 2024

Transition-metal-catalyzed directed C-H functionalization with various carbene precursors has been widely employed for constructing a wide range of complex and diverse active molecules through metal migratory insertion processes. Among precursors, iodonium ylides serve as novel emerging precursor features including easy accessibility, thermal stability high activity, which have attracted great attention from organic chemists achieved tremendous success in transformation. In this review, recent progress on the application multifunctional coupling characteristics bond activation reactions is summarized, potential discussed.

Language: Английский

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Rhodium-catalyzed annulation for the construction of indole core: An update

Tetrahedron, Journal Year: 2023, Volume and Issue: 146, P. 133633 - 133633

Published: Sept. 11, 2023

Language: Английский

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Tunable Rh(III)-Catalyzed C(sp²)–H Bond Functionalization of Aryl Imidates with Cyclic 1,3-Diones: Strategic Use of Directing Groups

Organic Letters, Journal Year: 2024, Volume and Issue: 26(37), P. 7885 - 7890

Published: Sept. 6, 2024

A tunable Rh(III)-catalyzed C(sp

Language: Английский

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Recent Advances in Functionalization of Aromatic C(sp²)—H Bonds Based on N-Nitroso Direction

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(12), P. 4157 - 4157

Published: Jan. 1, 2023

Language: Английский

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Synthesis of Substituted Pyrido[1,2‐a]benzimidazoles by Ruthenium‐Catalyzed C−H Bond Activation and Tandem Cyclization of 2‐Arylimidazo[1,2‐a]pyridines with Iodonium Ylides

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(34)

Published: July 15, 2023

Abstract Ruthenium‐catalyzed C−H bond activation and tandem cyclization of 2‐arylimidazo[1,2‐ a ]pyridines with iodonium ylides proceed efficiently. For the first time, easily available inexpensive ruthenium complex were employed to synthesize pyrido[1,2‐ ]benzimidazole derivatives in good yields under simple easy‐to‐operate conditions. Several primary mechanism investigations synthetic applications involving gram‐scale preparation, derivatization reactions transformation ylide generated situ have also been conducted.

Language: Английский

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Nitrene C−H Bond Insertion Approach to Carbazolones and Indolones, and a Reactivity Departure for 7‐Membered Analogues**

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(72)

Published: Sept. 26, 2023

A modular platform for facile access to 1,2,3,9-tetrahydro-4H-carbazol-4-ones (H4 -carbazolones) and 3,4-dihydrocyclopenta[b]indol-1(2H)-ones (H2 -indolones) is described. The requisite 6- 5-membered 2-arylcycloalkane-1,3-dione precursors were readily obtained through a Cu-catalyzed arylation of 1,3-cyclohexanediones or by ring expansion aryl succinoin derivatives. Enolization one carbonyl group in the diones, conversion leaving group, subsequent azidation gave 2-aryl-3-azidocycloalk-2-en-1-ones. This two-step, one-pot highly regioselective with unsymmetrically substituted 2-arylcyclohexane-1,3-diones. regioselectivity, which important single isomers 3,3-disubstituted carbazolones, was analyzed mechanistically computationally. Finally, Rh-catalyzed nitrene/nitrenoid insertion into ortho C-H bond moiety H4 -carbazolones H2 -indolones. One carbazolone elaborated an intermediate reported total synthesis N-decarbomethoxychanofruticosinate, (-)-aspidospermidine, (+)-kopsihainanine A. With 2-phenylcycloheptane-1,3-dione, prepared from cyclohexanone benzaldehyde, reaction accomplished. However, unexpectedly led labile but characterizable azirine rather than indole derivative. Computations performed understand differences reactivities 5- 6-membered 2-aryl-3-azidocycloalk-2-en-1-ones comparison 7-membered analogue, support structural assignment azirine.

Language: Английский

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Rh(III)-Catalyzed Synthesis of Isocoumarins via C–H Activation of Phenacyl Phosphoniums with Iodonium Ylides

Synthesis, Journal Year: 2023, Volume and Issue: 56(01), P. 47 - 54

Published: Nov. 23, 2023

Abstract A phosphonium-assisted C–H cyclization with iodonium ylides has been developed under redox-neutral rhodium(III) catalysis, offering a wide variety of valuable isocoumarins in moderate to good yields. This transformation proceeds through activation, carbene insertion, and nucleophilic addition processes. The reaction occurs low catalyst loading short time does not require an oxidant.

Language: Английский

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