Chemo-, regio- and enantioselective hydroformylation of trisubstituted cyclopropenes: access to chiral quaternary cyclopropanes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 29, 2024

Catalytic asymmetric synthesis of polysubstituted chiral cyclopropane presents a significant challenge in organic due to the difficulty enantioselective control. Here we report rhodium-catalyzed highly chemo-, regio- and hydroformylation trisubstituted cyclopropenes affording quaternary cyclopropanes. Importantly, easy made sterically bulky ligand L1 can effectively suppress hydrogenation decomposition reactions give cyclopropanes with high enantioselectivities for both aryl alkyl functionalized substrates. Control experiments computational studies reveal hindered well-defined pocket instead substrates bearing electron-withdrawing diester groups is important controlling enantioselectivity regioselectivity. Scale-up reaction follow-up diverse transformations are also presented. Density Functional theory (DFT) computations suggest that enantio-selectivities originate from cyclopropene insertion Rh-H bond. The regioselectivity found benefit presence more efficient noncovalent interactions (NCIs) manifesting form C–H···Cl, C–H···N, l.p(Cl)···π contacts. Transition-metal-catalyzed represents an atom-economic clean approach preparation aldehydes efficiency. Herein, authors

Язык: Английский

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CoH-catalyzed asymmetric remote hydroalkylation of heterocyclic alkenes: a rapid approach to chiral five-membered S- and O-heterocycles

Chemical Science, Год журнала: 2024, Номер 15(23), С. 8888 - 8895

Опубликована: Янв. 1, 2024

A highly efficient method achieves precise construction of alkyl chiral centers at remote C3-positions in five-membered S/O-heterocycles via cobalt-catalyzed asymmetric hydroalkylation heterocyclic alkenes.

Язык: Английский

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Catalytic Regio- and Enantioselective Hydroformylation of Trisubstituted Alkenes to Construct α-Quaternary Lactams

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(9), С. 7886 - 7896

Опубликована: Фев. 24, 2025

Developing novel stereoselective methods for α-quaternary lactams is of significant importance advancing structure-activity studies, discovering new antibiotics, and synthesizing diverse functional compounds synthetic materials research. Herein, we have successfully developed a Rh-catalyzed asymmetric hydroformylation (AHF) trisubstituted olefins, overcoming both the inherent inertness olefins in such reactions Keulemans' rule, efficiently generating β- γ-lactams bearing an stereocenter with exceptional regio- enantioselectivities (up to >20:1 rr, 99% ee). This mild operationally simple reaction proceeds atom-economic manner broad substrate scope, along excellent functional-group tolerance, scalability, product diversification. Computational studies suggest that enantio- and/or regioselectivity may originate from Rh-C bonding noncovalent interactions between Boc group on Ph groups ligand.

Язык: Английский

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Nickel-Catalyzed Branched Hydroalkylation of Alkenes with Diazo Compounds

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

Опубликована: Фев. 25, 2025

A nickel-catalyzed, branched-selective hydroalkylation of alkenes using diazo compounds has been developed. This protocol enables the functionalization both activated and unactivated alkenes, in directed nondirected manners. Mono-, di-, trisubstituted can be effectively transformed. Highly diastereoselective hydroalkylations have also demonstrated. The method provides a novel approach for introducing an α-carbonyl moiety to which is currently inaccessible by existing methods. Preliminary mechanistic investigations suggest carbene-type mechanism, unusual nickel catalysis.

Язык: Английский

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Isomerization and Hydroformylation of Long‐Chain Olefins Promoted by N^O Bidentate Rh(I) Catalysts Precursors Bearing Salicylaldimine and Naphthaldimine Supporting Ligands

Applied Organometallic Chemistry, Год журнала: 2025, Номер 39(4)

Опубликована: Март 3, 2025

ABSTRACT A series of Schiff‐base rhodium(I) complexes ( C1 – C8 ) chelating N^O salicylaldimine and naphthaldimine ligands have been synthesized characterized. These were evaluated for their ability to catalyse the isomerization hydroformylation terminal (1‐octene 1‐decene) internal olefins (1, 2‐, 3‐, 4‐octene) linear branched aldehydes. The pre‐catalysts resulted in excellent substrate conversion (> 99%) with 100% chemoselectivity towards aldehydes, under mild conditions. Good regioselectivities aldehydes observed from olefins, clearly demonstrating catalysts' thermodynamically favoured followed by (n/iso ratio ranging between 0.52 0.67).

Язык: Английский

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Rhodium‐Catalyzed Chemo‐, Regio‐ and Enantioselective Hydroformylation of Cyclopropyl‐Functionalized Trisubstituted Alkenes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(33)

Опубликована: Июнь 18, 2022

The first rhodium-catalyzed highly chemo-, regio- and enantioselective hydroformylation of cyclopropyl-functionalized trisubstituted alkenes affording useful chiral cyclopropyl entities is reported. Compared to generally used diphosphine ligands for asymmetric catalysis, the modified hybrid phosphorus ligand, named (R,S)-DTBM-Yanphos, can convert a series readily available into high-value aldehydes with high selectivities (81-98 % ee). Gram-scale reactions (TON up 1500) follow-up transformations corresponding alcohol, acid, esters nitrile are also presented. Finally, possible mechanism involving ring-open-hydroformylation pathways proposed based on control deuteroformylation reactions.

Язык: Английский

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Rapid microwave synthesis of Bi2WO6 for C=C bonds oxidative cleavage to ketones with visible light irradiation in aerobic micellar medium

Journal of Catalysis, Год журнала: 2022, Номер 417, С. 41 - 51

Опубликована: Ноя. 27, 2022

Язык: Английский

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Multicomponent coupling and macrocyclization enabled by Rh(III)-catalyzed dual C–H activation: Macrocyclic oxime inhibitor of influenza H1N1

Chem, Год журнала: 2022, Номер 9(3), С. 607 - 623

Опубликована: Ноя. 10, 2022

Язык: Английский

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Regio- and Enantioselective Hydromethylation of 3-Pyrrolines and Glycals Enabled by Cobalt Catalysis

JACS Au, Год журнала: 2024, Номер 4(6), С. 2312 - 2322

Опубликована: Июнь 11, 2024

Enantioenriched 3-methylpyrrolidine, with its unique chiral nitrogen-containing core skeleton, exists widely in various functional molecules, including natural products, bioactive compounds, and pharmaceuticals. Traditional methods for synthesizing these valuable methyl-substituted heterocycles often involve enzymatic processes or complex procedures auxiliaries, limiting the substrate scope efficiency. Efficient catalytic methylation, especially an enantioselective manner, has been a long-standing challenge chemical synthesis. Herein, we present novel approach remote stereoselective installation of methyl group onto N-heterocycles, leveraging CoH-catalyzed asymmetric hydromethylation strategy. By effectively combining commercial cobalt precursor modified bisoxazoline (BOX) ligand, variety easily accessible 3-pyrrolines can be converted to enantiopure 3-(isotopic labeling)methylpyrrolidine compounds outstanding enantioselectivity. This efficient protocol streamlines two-step synthesis enantioenriched which previously required up five six steps under harsh conditions expensive starting materials.

Язык: Английский

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Water-soluble diphosphine ligands for rhodium-catalyzed branch-selective hydroaminomethylation of vinyl arenes with anilines in water

Green Chemistry, Год журнала: 2022, Номер 24(11), С. 4420 - 4424

Опубликована: Янв. 1, 2022

Rhodium-catalyzed hydroaminomethylation of various vinyl arenes with anilines has been accomplished using water as an environmentally benign reaction media.

Язык: Английский

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