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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Photoredox-Catalyzed Alkylamination of Alkenes via Oxidative Radical-Polar Crossover and Site-Selective 1,5-Hydrogen Atom Transfer

Organic Letters, Год журнала: 2024, Номер 26(32), С. 6847 - 6852

Опубликована: Авг. 7, 2024

We reported the visible-light-mediated photoredox-catalyzed oxidative radical-polar crossover and 1,5-hydrogen atom transfer combined site-selective remote C(sp

Язык: Английский

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Photocatalyzed Azidofunctionalization of Alkenes via Radical‐Polar Crossover

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Янв. 2, 2025

The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical-polar crossover strategy. A broad range alkenes, including vinyl arenes, enamides, enol ethers, sulfides, dehydroamino esters, were regioselectively functionalized with an azide nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric oximes, phenols. method led to more efficient synthesis 1,2-azidofunctionalized pharmaceutical intermediates when compared previous approaches, resulting in both reduction step count increase overall yield. scope limitations these transformations further investigated through standard unbiased selection 15 substrate combinations out 1,175,658 possible clustering technique.

Язык: Английский

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Photocatalyzed Azidofunctionalization of Alkenes via Radical‐Polar Crossover

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Янв. 2, 2025

Abstract The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical‐polar crossover strategy. A broad range alkenes, including vinyl arenes, enamides, enol ethers, sulfides, dehydroamino esters, were regioselectively functionalized with an azide nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric oximes, phenols. method led to more efficient synthesis 1,2‐azidofunctionalized pharmaceutical intermediates when compared previous approaches, resulting in both reduction step count increase overall yield. scope limitations these transformations further investigated through standard unbiased selection 15 substrate combinations out 1,175,658 possible clustering technique.

Язык: Английский

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Photoredox-Catalyzed Three-Component Sulfonaminoalkynylation of Alkenes via a Radial/Polar Crossover

The Journal of Organic Chemistry, Год журнала: 2025, Номер 90(4), С. 1656 - 1662

Опубликована: Янв. 21, 2025

We report a photoredox-catalyzed three-component sulfonaminoalkynylation of alkenes with N-aminopyridine salts and potassium alkynyltrifluoroborate salts. This aminoalkylation reaction underwent radial/polar crossover mechanism, which was distinguished from the previous reports. A variety β-alkynylated sulfonamides were obtained in moderate to excellent yields. The versatility this method further evidenced by its successful application modifying biological molecules advanced stages development.

Язык: Английский

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Visible-Light-Induced 4CzIPN-Catalyzed Alkylamination of Alkenes via Cyclobutanone Oxime Esters and Anilines

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 22, 2025

We disclosed an organophotoredox-catalyzed three-component oxidative radical-polar crossover strategy for constructing 1,2-alkylamination products. Cycloketone oxime derivatives were used as cyanoalkyl radical precursors and anilines the nucleophiles. This facile protocol shows a good reaction yield broad substrate scope.

Язык: Английский

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Copper-Catalyzed Selective Three-Component 1,2-Phosphonoazidation of 1,3-Dienes

Organic Letters, Год журнала: 2024, Номер 26(7), С. 1387 - 1392

Опубликована: Фев. 11, 2024

We report a copper-catalyzed selective 1,2-phosphonoazidation of conjugated dienes. This three-component reaction is achieved by using readily available P(O)–H compounds and bench-stable NaN3. Salient features this strategy include its mild conditions, broad functional group tolerance, high chemoselectivity regioselectivity. Moreover, the compatibility with late-stage functionalization drug molecules, potential for scalable production, feasibility further modifications products underscore practical utility protocol in synthetic applications.

Язык: Английский

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SOMOphilic alkyne vs radical-polar crossover approaches: The full story of the azido-alkynylation of alkenes

Beilstein Journal of Organic Chemistry, Год журнала: 2024, Номер 20, С. 701 - 713

Опубликована: Апрель 3, 2024

We report the detailed background for discovery and development of synthesis homopropargylic azides by azido-alkynylation alkenes. Initially, a strategy involving SOMOphilic alkynes was adopted, but only resulted in 29% yield desired product. By switching to radical-polar crossover approach after optimization, high (72%) azide reached. Full insights are given about factors that were essential success optimization process.

Язык: Английский

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New chemistry of alkynyl trifluoroborates under transition metal catalyst-free conditions

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(20), С. 5985 - 6003

Опубликована: Янв. 1, 2024

This review summarizes recent advances in alkynyl trifluoroborate chemistry, emphasizing their unique reactivity and stability organic synthesis biological applications under transition metal catalyst-free conditions.

Язык: Английский

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Photocatalytic Decarboxylative Functionalization of Cyclopropenes via Cyclopropenium Cation Intermediates

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(32)

Опубликована: Май 28, 2024

Abstract A photocatalytic decarboxylative functionalization of cyclopropenes is reported. Starting from a broad range redox‐active ester‐substituted cyclopropenes, cyclopropenylphthalimides can be synthesized in the absence nucleophile. Alternatively, different carbon and heteroatom nucleophiles introduced. The transformation proceeds most probably through formation an aromatic cyclopropenium cation, followed by trapping with nucleophiles.

Язык: Английский

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