Development of a Phototriggered Diradical Phosphoamination Strategy of Alkenes

Organic Letters, Год журнала: 2025, Номер 27(2), С. 606 - 611

Опубликована: Янв. 6, 2025

Aminophosphonates serve as extremely important moieties with respect to their activities in biological systems. However, incorporating a Nitrogen and Phosphorus moiety by conventional techniques ionic mode is usually associated extensive prefunctionalization of the substrates, employing harsh conditions reagents that limit viability these methods. Introducing both components radicals may be viable option. We hereby propose an overhaul existing reactivity paradigm demonstrating photocatalytic diradical-based approach, where new iminophosphonating are rationally designed developed used extensively homolytic cleavage for simultaneously installing iminyl phosphonyl groups onto alkenes.

Язык: Английский

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Rhodium‐Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of 1,3‐Dipolar Nitrones

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 17, 2024

Abstract Owing to their distinctive 1,3‐dipolar structure, the catalytic asymmetric hydrogenation of nitrones hydroxylamines has been a formidable and longstanding challenge, characterized by intricate enantiocontrol susceptibility N−O bond cleavage. In this study, transfer were accomplished with tethered TsDPEN‐derived cyclopentadienyl rhodium(III) catalyst (TsDPEN: p ‐toluenesulfonyl‐1,2‐diphenylethylene‐1,2‐diamine), reaction proceeds via novel 7‐membered cyclic transition state, producing chiral up 99 % yield >99 ee. The practical viability methodology was underscored gram‐scale reactions subsequent transformations. Furthermore, mechanistic investigations DFT calculations also conducted elucidate origin enantioselectivity.

Язык: Английский

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Construction of C–P Bonds from Free Cyclobutanone Oximes and Chlorophosphines via Radical–Radical Coupling

Organic Letters, Год журнала: 2024, Номер 26(15), С. 3208 - 3212

Опубликована: Апрель 10, 2024

Herein, we report a catalyst-free reaction of cyclobutanone oximes with chlorophosphines (R2PCl), which forms fragile C═N–O–PR2 species that undergoes N–O homolysis, fragmentation, and radical–radical coupling, leading to the formation cyano-containing phosphine oxides in good yields. The features an situ activation for radical generation, R2PCl plays dual role as both activator reactant.

Язык: Английский

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CuH-Catalyzed Reductive Coupling of Nitroarenes with Phosphine Oxides for the Direct Synthesis of Phosphamides

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(11), С. 7848 - 7858

Опубликована: Май 29, 2024

A CuH-catalyzed reductive coupling of nitroarenes with phosphine oxides is developed, which produces a series phosphamides in moderate to excellent yields good functional group tolerance. Gram-scale synthesis and late-stage modification nitro-aromatic molecule niclosamide are also successfully conducted. The mechanism study shows that the nitro transformed after being reduced nitroso nucleophilic addition procedure involved during reaction.

Язык: Английский

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Selective Functionalization of C(sp³)—H Bonds via Photoredox/ Nickel Dual Catalysis

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(2), С. 383 - 383

Опубликована: Янв. 1, 2025

Язык: Английский

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Harnessing Nitroarenes: Photo-Driven Synergistic Construction of Phosphinic Amides via Hydrogen Transfer and Oxygen Migration

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A method for synthesizing phosphinic amides via hydrogen transfer and oxygen migration through an EDA complex-based cascade reaction is presented.

Язык: Английский

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Tf₂O-Mediated P(O)–N Bond Formation of Either P(O)–OH or P(O)–H Reagents with Multitype Amines

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(10), С. 6729 - 6739

Опубликована: Май 1, 2024

We have developed a Tf2O-mediated approach for the direct amination of either P(O)–OH or P(O)–H reagents with variety aliphatic aromatic amines. Without requirement precious metals and toxic reagents, this protocol provides an alternative route to various phosphinamides phosphoramides. The reaction proceeds under simple mild conditions can be effectively scaled up similar efficiency.

Язык: Английский

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Rhodium‐Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of 1,3‐Dipolar Nitrones

Angewandte Chemie, Год журнала: 2024, Номер 136(14)

Опубликована: Фев. 17, 2024

Abstract Owing to their distinctive 1,3‐dipolar structure, the catalytic asymmetric hydrogenation of nitrones hydroxylamines has been a formidable and longstanding challenge, characterized by intricate enantiocontrol susceptibility N−O bond cleavage. In this study, transfer were accomplished with tethered TsDPEN‐derived cyclopentadienyl rhodium(III) catalyst (TsDPEN: p ‐toluenesulfonyl‐1,2‐diphenylethylene‐1,2‐diamine), reaction proceeds via novel 7‐membered cyclic transition state, producing chiral up 99 % yield >99 ee. The practical viability methodology was underscored gram‐scale reactions subsequent transformations. Furthermore, mechanistic investigations DFT calculations also conducted elucidate origin enantioselectivity.

Язык: Английский

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Effect of Substituents in Governing the Homolytic Gas-Phase P–H Bond Dissociation Enthalpies of Phosphine-type Oxides (R1R2P(=O)H)

Chemical Data Collections, Год журнала: 2024, Номер unknown, С. 101164 - 101164

Опубликована: Сен. 1, 2024

Язык: Английский

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A Protocol for the Synthesis of Organophosphorus(V) Compounds with P–N and P–O Bonds by Umpolung Strategy Using Hydroxymethylphosphine Sulfides

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Дек. 19, 2024

Versatile P-N and P-O bond-forming reactions by an umpolung approach using air- moisture-stable hydroxymethylphosphine sulfides were developed. Phosphine containing multiple hydroxymethyl groups could undergo sequential transformations combining as well P-C bond formations, providing a novel protocol for the synthesis of variety organophosphorus(V) compounds with bonds.

Язык: Английский

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