Reductive Coupling of P(O)–H Compounds and Aldehydes for the General Synthesis of Phosphines and Phosphine Oxides

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(7), С. 5109 - 5117

Опубликована: Март 14, 2024

A novel strategy for the selective construction of a C(sp3)–P(III) or −P(V) bond from >P(O)–H compounds and aldehydes is disclosed. By using H3PO3/I2 system, various secondary phosphine oxides could react with both aromatic aliphatic to afford valuable phosphines (isolated as sulfides) in good yields. This method features wide substrate scope simple reaction conditions avoids use toxic halides metals.

Язык: Английский

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Phosphonium-Catalyzed Monoreduction of Bisphosphine Dioxides: Origin of Selectivity and Synthetic Applications

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9335 - 9346

Опубликована: Март 19, 2024

Controlling product selectivity in successive reactions of the same type is challenging owing to comparable thermodynamic and kinetic properties involved. Here, synergistic interaction two phosphoryl groups bisphosphine dioxides (BPDOs) with a bromo-phosphonium cation was studied experimentally provide practical tool for substrate–catalyst recognition. As eventual result, we have developed phosphonium-catalyzed monoreduction chiral BPDOs access an array synthetically useful monoxides (BPMOs) axial, spiro, planar chirality, which are otherwise synthesize before. The reaction features excellent impressive reactivity. It proceeds under mild conditions, avoiding use superstoichiometric amounts additives metal catalysts simplify synthetic procedure. accessibility scalability allowed rapid construction ligand library optimization asymmetric Heck-type cyclization, laying foundation broad range applications BPMOs catalysis.

Язык: Английский

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Regioselective One-Pot Synthesis of Vicinal Bisphosphine Derivatives from Nitroalkenes by Hydrophosphinylation/Elimination/Hydrophosphinylation

Organic Letters, Год журнала: 2024, Номер 26(9), С. 1797 - 1802

Опубликована: Фев. 23, 2024

Herein, a facile method is developed for the synthesis of vicinal bisphosphine derivatives based on cascade hydrophosphinylation, elimination, and hydrophosphinylation secondary phosphine oxides with nitroalkenes. This reaction provides step-economy access to series high excellent yields (up 99%). was further extended prepare, in one-pot, regioselective that incorporated two different phosphorus functional groups.

Язык: Английский

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Combined Computational and Experimental Study Reveals Complex Mechanistic Landscape of Brønsted Acid-Catalyzed Silane-Dependent P═O Reduction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(20), С. 13983 - 13999

Опубликована: Май 13, 2024

The reaction mechanism of Brønsted acid-catalyzed silane-dependent P═O reduction has been elucidated through combined computational and experimental methods. Due to its remarkable chemo- stereoselective nature, the acid/silane system widely employed in organophosphine-catalyzed transformations involving P(V)/P(III) redox cycle. However, full mechanistic profile this type yet be clearly established date. Supported by both DFT studies, our research reveals that likely proceeds mechanisms other than accepted "dual activation mode silyl ester" or "acid-mediated direct activation" mechanism. We propose although may vary with substitution patterns silane species, acid generally activates rather group transition structures. proposed differs significantly from associated traditional C═O reduction. uniqueness originates dominant Si/O═P orbital interactions structures P/H–Si interactions. comprehensive landscape provided us will serve as a guidance for rational design development more efficient systems well novel reactions

Язык: Английский

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Palladium-catalyzed coupling of aryl sulfonium salts with [TBA][P(SiCl3)2] for the construction of tertiary phosphines

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

We present a strategy for the synthesis of triarylphosphines via palladium-catalyzed C–P cross-coupling reactions aryl sulfonium salts with [TBA][P(SiCl 3 ) 2 ].

Язык: Английский

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Selective C(sp²)–P Cross-Coupling of Alkenylsulfonium Salts with P(O)H Compounds: Divergent Synthesis of Alkenylphosphorus Compounds

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 13, 2025

Herein, we report a both regioselective and stereoselective method for the formation of C(sp2)–P bonds using alkenylsulfonium salts >P(O)–H compounds. By employing palladium catalyst or K2CO3, variety (E)-alkenylphosphorus compounds terminal alkenylphosphorus were successfully synthesized with high selectivity. Notably, trisubstituted (Z)-alkenylphosphorus first time under metal-free conditions. This protocol has wide substrate scope good functional group compatibility, providing direct highly selective approach preparation various

Язык: Английский

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Metal‐Free Formation of Xanthenes and Xanthones from 2‐aryloxybenzaldehydes via Intramolecular Cyclization

ChemistrySelect, Год журнала: 2025, Номер 10(14)

Опубликована: Апрель 1, 2025

Abstract We herein report a metal‐free strategy for the selective synthesis of xanthenes and xanthones from 2‐aryloxybenzaldehydes. By employing phosphorous acid/iodine system, we achieved efficient preparation diverse via intramolecular reductive cyclization. In contrast, series were constructed same substrates through TBAI‐catalyzed direct This methodology offers notable advantages, including straightforward workup, absence metal involvement, low‐cost. A plausible reaction mechanism was also proposed.

Язык: Английский

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Tertiary Amine-Mediated Reductions of Phosphine Oxides to Phosphines

Organic Letters, Год журнала: 2023, Номер 25(28), С. 5236 - 5241

Опубликована: Июль 10, 2023

The reduction of phosphine oxides without the use highly reactive reductants represents a safer and more sustainable solution for recycling organophosphorus compounds. Herein, we disclose an N,N,N',N'-tetramethylethylenediamine (TMEDA)-mediated via unusual intermolecular hydride transfer. Mechanistic studies suggest that TMEDA serves as donor, while P(V) halophosphonium salt acts acceptor. This methodology provides scalable efficient protocol to reduce under mild conditions.

Язык: Английский

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Advances in Organic Reactions Using Phosphorus Acid as Reducing Agent

Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(12), С. 3702 - 3702

Опубликована: Янв. 1, 2024

Язык: Английский

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Restoration of triphenylphosphine using the “sulfur method”: two valuable chemicals from waste products

Green Chemistry, Год журнала: 2023, Номер 25(22), С. 9063 - 9068

Опубликована: Янв. 1, 2023

Ph 3 P is found to be inert sodium in toluene even on heating.

Язык: Английский

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