Kinetic Resolution of α,β-Unsaturated Tertiary Phosphine Oxides via Alkene E → Z Isomerization Catalyzed by a Photoexcited Chiral Copper Complex

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4541 - 4549

Опубликована: Март 3, 2025

Язык: Английский

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Construction of Vicinal All-Carbon Stereogenic Centers via Copper-Catalyzed Asymmetric Decarboxylative Propargylation: Enantio- and Diastereoselective Synthesis of Substituted Spirolactones

Organic Letters, Год журнала: 2023, Номер 25(2), С. 410 - 415

Опубликована: Янв. 11, 2023

The formation of vicinal all-carbon quaternary stereocenters remains a formidable challenge. We report herein the synthesis such highly congested structural dyads by copper-catalyzed decarboxylative propargylation between propargyl carbonates and indanone-based nucleophiles. implementation diphenylethylenediamine (DPEN)-based ligands is key to success. A wide range functional groups was tolerated, delivering spirolactones in good yields with high diastereo- enantioselectivity. mechanistic observations suggest capability new copper complex enable stereocontrolled addition copper-allenylidene species.

Язык: Английский

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P^III/P^V═O Redox Catalysis Mediated Thioesterification of Carboxylic Acids with Disulfides under Air Conditions

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

Опубликована: Янв. 12, 2025

An efficient organophosphorus-catalyzed thiocarbonylation reaction of disulfides with carboxylic acids under air conditions was described. Various functional groups on and can be tolerated the present conditions, affording thioesters in good to excellent yields. This method exhibited chemoselectivity applied for late-stage functionalization drug molecules containing a acid group.

Язык: Английский

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Multigram-Scale Synthetic Routes to Solvent-Free Common Secondary Dialkylphosphines and Chlorodialkylphosphines

Organometallics, Год журнала: 2025, Номер unknown

Опубликована: Фев. 20, 2025

Язык: Английский

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The Outstanding Ambiphilicity of Trialkylstibines among Trialkylpnictines: Power for Stepwise Deoxygenation and N–N Coupling of Nitroarenes

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

The ongoing discovery of highly reactive ambiphilic main-group species has significantly advanced the development chemistry, particularly in realms small molecule activation and catalysis. Theoretically, compounds featuring smaller HOMO–LUMO gaps gain stronger ambiphilicity higher reactivity. In this work, we fundamentally demonstrate that Me3Sb holds smallest gap among trimethylpnictines, indicating its outstanding ambiphilicity. Correspondingly, superior reactivity toward deoxygenation electron-deficient nitroarenes been unambiguously revealed through control experiments. Furthermore, unprecedented SbIII/SbVO cycling between trialkylstibines their oxides established for catalytic transformation into azoxyarenes/azoarenes. This study opens a new chapter organoantimony derivatives fields redox

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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Water-Controlled Geminal Hydroxyphosphinoylation and Diphosphinoylation of Enaminones with H-Phosphine Oxides

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

Опубликована: Март 6, 2025

A water-controlled geminal phosphinoylation of enaminones with H-phosphine oxides has been established through AlCl3-mediated C-N bond cleavage in this work, which provides a novel strategy for accessing various hydroxy and diphosphinoyl products 3a 4a high yields. The transformation features excellent functional group tolerance, operational simplicity, atom economy, is amenable complex molecule skeletons. Preliminary mechanism studies suggest the conversion from to involve elimination hydroxyl group, water temperature plays critical role influencing reaction pathway product selectivity. This research significant value functionalization enaminones.

Язык: Английский

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Innovative strategies for organophosphorus remediation: Integrating enzymatic decomposition with membrane technologies

Results in Chemistry, Год журнала: 2025, Номер unknown, С. 102298 - 102298

Опубликована: Апрель 1, 2025

Язык: Английский

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Antimony Redox Catalysis: Hydroboration of Disulfides through Unique Sb(I)/Sb(III) Redox Cycling

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(29), С. 20432 - 20438

Опубликована: Июль 9, 2024

The stibinidene ArSb

Язык: Английский

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Recent Advances in Asymmetric Synthesis of P-Chiral Phosphine Oxides

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(6), С. 1963 - 1963

Опубликована: Янв. 1, 2023

Enantioenriched organophosphates are ubiquitous in a large array of chiral ligands, catalysts and bioactive molecules.Over the past few decades, synthetic chemists have contributed substantial efforts to develop efficient methodologies for construction P-chiral phosphine derivatives, considerably enriching arsenal organophosphine ligands promising pharmaceutical molecules.Among them, number works focused on synthesis oxides because it is more stability than trivalent phosphines convenient reduction.In view rapid progress this area currently available reviews, last three years summarized discussed, namely from 2020 2022.The description strategy divided into five segments, involving asymmetric induction, catalytic desymmetrization, synthesis, kinetic resolution or dynamic transformation, enzyme catalysis.

Язык: Английский

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