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

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Сен. 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.

Язык: Английский

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

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(16), С. 2653 - 2675

Опубликована: Апрель 21, 2023

Abstract Hypervalent iodine compounds have found broad application in modern organic chemistry as reagents and catalysts. Cyclic hypervalent based on the benziodoxole heterocyclic system higher stability compared to their acyclic analogues, which makes possible preparation safe handling of with special ligands such azido, cyano, trifluoromethyl groups. Numerous iodine‐substituted derivatives been prepared utilized for transfer substituent substrate. Reactions these substrates can be performed under metal‐free conditions, presence transition metal catalysts, or using photocatalysts photoirradiation conditions. In this review, we focus most recent synthetic applications cyclic iodine(III) following ligands: N 3 , NHR, CN, CF SCF OR, OAc, ONO 2 C(=N )CO R. The review covers literature published mainly last 5 years.

Язык: Английский

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Carboiodanation of Arynes: Organoiodine(III) Compounds as Nucleophilic Organometalloids

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(6), С. 3910 - 3919

Опубликована: Фев. 5, 2024

Organic iodine(III) compounds represent the most widely used hypervalent halogen in organic synthesis, where they typically perform role of an electrophile or oxidant to functionalize electron-rich -nucleophilic compounds. In contrast this convention, we discovered their unique reactivity as organometallic-like nucleophiles toward arynes. Equipped with diverse transferable ligands and supported by a tethered spectator ligand, organoiodine(III) undergo addition across electrophilic C–C triple bond arynes while retaining trivalency iodine center. This carboiodanation reaction can forge variety aryl–alkynyl, aryl–alkenyl, aryl–(hetero)aryl bonds along concurrent formation aryl–iodine(III) under mild conditions. The newly formed serves versatile linchpin for downstream transformations, particularly site. amphoteric nature group metalloid leaving sequence enables flexible expedient synthesis extended π-conjugated molecules privileged biarylphosphine ligands, all iodine(III)-containing be handled air- thermally stable materials.

Язык: Английский

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Dibenzothiophenium Salts: Practical Alternatives to Hypervalent I(III)-Based Reagents

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 2, 2025

ConspectusDuring the past few years, interest among organic synthesis practitioners in use of sulfonium salts has exponentially growth. This can arguably be attributed to a series specific factors: (a) The recent development more direct and efficient protocols for these species, which make reagents wide structural variety easily available multigram scale. (b) recognition that reactivity resembles hypervalent iodine compounds, therefore, they used as effective replacement such species most their applications. (c) Their intrinsic thermal stability tolerance air moisture, clearly surpass I(III)-reagents analogue reactivity, facilitate purification, isolation well-defined storage, safely handling on larger (d) Finally, possibility further functionalize once sulfur-containing platform been incorporated. Specifically, this last synthetic approach is not trivial when working with I(III)-species facilitates access no counterpart I(III) realm.This renewed led improvement already existing transformations well discovery unprecedented ones; particular, by incorporate partners traditional cross-coupling C–H activation steps or combine them modern technologies photocatalysis electrosynthesis. In Account, originally prepared our laboratory will outlined compared I(III)-counterparts. Some are now commercially available, started spread widely across chemistry community, helping speed process identification potentially bioactive products new functionaliced materials. However, challenges still remain. characterized an optimal balance between site-selectivity, showing broader compatibility toward sensitive functional groups need. addition, often makes necessary (sophisticated) catalysts activate latent hidden structures. Although priori one see fact disadvantage, it might actually decisive harvest full potential because surely preparation operational context I(III)-chemistry. If becomes true, may contribute expediting retrosynthetic disconnections that, date, impossible.

Язык: Английский

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Aryl-, Akynyl-, and Alkenylbenziodoxoles: Synthesis and Synthetic Applications

Molecules, Год журнала: 2023, Номер 28(5), С. 2136 - 2136

Опубликована: Фев. 24, 2023

Hypervalent iodine reagents are in high current demand due to their exceptional reactivity oxidative transformations, as well diverse umpolung functionalization reactions. Cyclic hypervalent compounds, known under the general name of benziodoxoles, possess improved thermal stability and synthetic versatility comparison with acyclic analogs. Aryl-, alkenyl-, alkynylbenziodoxoles have recently received wide applications efficient for direct arylation, alkenylation, alkynylation mild reaction conditions, including transition metal-free conditions photoredox metal catalysis. Using these reagents, a plethora valuable, hard-to-reach, structurally complex products can be synthesized by convenient procedures. The review covers main aspects chemistry benziodoxole-based aryl-, alkynyl-, alkenyl- transfer preparation applications.

Язык: Английский

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Organohypervalent heterocycles

Chemical Society Reviews, Год журнала: 2024, Номер 53(9), С. 4786 - 4827

Опубликована: Янв. 1, 2024

This review summarizes structural and synthetic aspects of heterocyclic molecules incorporating an atom a hypervalent main-group element. The higher thermal stability heterocycles, as compared to their acyclic analogs, adds special feature chemistry.

Язык: Английский

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Boryl Radical-Mediated Halogen-Atom Transfer (XAT) Enables the Sonogashira-Like Alkynylation of Alkyl Halides

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

The Sonogashira-like alkynylation of alkyl halides is achieved by a photocatalytic approach exploiting amine-ligated boryl radicals as halogen-atom transfer mediators in combination with alkynyl sulfones SOMOphilic reagents.

Язык: Английский

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The Application of Benziodazole-Type O₂NO-I(III) Compound as a Nitrating Reagent for Nitration of Phenols and Anilines

The Journal of Organic Chemistry, Год журнала: 2025, Номер 90(6), С. 2328 - 2340

Опубликована: Янв. 31, 2025

A benziodazole-type O2NO-I(III) compound was used as a nitrating reagent to react with series of electron-rich arenes including substituted phenols and anilines, affording the corresponding nitration products under mild conditions. Mechanistically, generates reactive nitrogen dioxide (NO2) species, which enables anilines.

Язык: Английский

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Advances in Catalytic Enantioselective Transformations Using Diaryliodonium Reagents

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3096 - 3115

Опубликована: Фев. 5, 2025

Язык: Английский

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Alkynyl Radicals, Myths and Realities

JACS Au, Год журнала: 2025, Номер 5(2), С. 448 - 465

Опубликована: Фев. 6, 2025

This Perspective deals with the organic chemistry of alkynyl radicals, a species that is ultimately still little known in synthetic community. Starting first observations and characterizations radicals generated by various methodologies gas phase, we then particularly turned our attention to implications these highly reactive intermediates synthesis materials science. Mechanistic considerations have been provided, particular, for key steps generating which are mainly based on photochemical or thermal activation single electron transfer processes. should serve as roadmap chemist order plan more reliably alkynylation reactions radicals.

Язык: Английский

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