Palladium‐Catalyzed Fluorinative Bifunctionalization of Aziridines and Azetidines with gem‐Difluorocyclopropanes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(42)

Опубликована: Авг. 12, 2023

Abstract An unprecedented Pd‐catalyzed fluorinative bifunctionalization of aziridines and azetidines was successfully developed via regioselective C−C C−F bond cleavage gem‐difluorocyclopropanes, leading to various β,β′‐bisfluorinated amines β,γ‐bisfluorinated amines. This reaction achieved by incorporating a 2‐fluorinated allyl group fluorine atom scissored from gem‐difluorocyclopropane in 100 % economy for the first time. The mechanistic investigations indicated that underwent amine attacking palladium complex generate η 2 ‐coordinated N‐allyl aziridine followed fluoride ligand transfer affording final β‐ γ‐fluorinated

Язык: Английский

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Asymmetric Transfer Hydrogenation of Cyclobutenediones

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4942 - 4957

Опубликована: Фев. 7, 2024

Four-membered carbocycles are fundamental substructures in bioactive molecules and approved drugs serve as irreplaceable building blocks organic synthesis. However, developing efficient protocols furnishing diversified four-membered ring compounds a highly regio-, diastereo-, enantioselective fashion remains challenging but very desirable. Here, we report the unprecedented asymmetric transfer hydrogenation of cyclobutenediones. The reaction can selectively afford three types products high yields with stereoselectivities, functionalized enable series further transformations to form more compounds. Asymmetric synthesis di-, tri-, tetrasubstituted has also been achieved. Systematic mechanistic studies theoretical calculations have revealed origin regioselectivity, key transition state models, sequence double triple processes. work provides new choice for catalytic cyclobutanes related structures demonstrates robustness accurate selectivity control substrates.

Язык: Английский

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Selectivity in Rh-catalysis with gem-difluorinated cyclopropanes

Chemical Communications, Год журнала: 2024, Номер 60(28), С. 3764 - 3773

Опубликована: Янв. 1, 2024

This feature article summarizes our efforts towards developing Rh-catalyzed reactions of gem -difluorinated cyclopropanes, briefly discussing the design, selectivity, mechanisms and future research prospects.

Язык: Английский

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Rh-Catalyzed Formal [3 + 2] Cycloaddition Reactions with Cyclopropenones via Sequential C–H/C–C Bond Activation

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 13, 2025

The utilization of high-valent metal catalysts to promote cycloaddition reactions involving π bonds through C-C bond activation remains challenging. Despite extensive research, the aldehydes with cyclopropenones catalyzed by complexes has not been documented. Herein, we disclose a novel Rh(III)-catalyzed reaction between and aldehydes, enabling efficient synthesis highly functionalized furanones. A detailed mechanistic investigation was conducted, revealing likely involvement tripodal Rh-carbene intermediate in catalytic cycle, which facilitates product release pathway. This exhibits broad substrate scope, good functional group compatibility, high atom economy, thereby offering versatile general approach construction

Язык: Английский

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Palladium-Catalyzed Skeletal Rearrangement of Cyclobutanones via C–H and C–C Bond Cleavage

ACS Catalysis, Год журнала: 2023, Номер 13(4), С. 2234 - 2239

Опубликована: Янв. 27, 2023

The palladium-catalyzed skeletal rearrangement of 3-arylcyclobutanones into 1-indanones is reported. A Pd(0)/IMes catalyst allows for the cleavage C(carbonyl)–C(sp3) and C(sp2)–H bonds to result in rearrangement, neither an extra reactive functional group nor a directing required promote reaction. Deuterium-labeling experiments indicate that C–C bond initially activated subsequent C–H activation involved rate-determining step.

Язык: Английский

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Palladium-Catalyzed Cross-Coupling of gem-Difluorocyclopropanes with gem-Diborylalkanes for the Synthesis of Boryl-Substituted Fluorinated Alkenes

Organic Letters, Год журнала: 2023, Номер 25(50), С. 9020 - 9024

Опубликована: Дек. 8, 2023

This study presents a novel method for the regioselective coupling of gem-difluorinated cyclopropanes with gem-diborylmethane, utilizing Pd-catalyst system. innovative approach enables synthesis 2-fluoroalkenyl monoboronate scaffolds high Z-selectivity. The resulting products undergo further transformations, including oxidation, Suzuki cross-coupling, and trifluoroborylation, all which are achieved good yields. work introduces valuable synthetic pathway to access important fluorinated compounds various applications in organic chemistry.

Язык: Английский

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Ring‐Opening Cross‐Coupling/Cyclization Reaction of Cyclopropanols with Organic Compounds

ChemistrySelect, Год журнала: 2023, Номер 8(32)

Опубликована: Авг. 23, 2023

Abstract Cyclopropanols, due to their particular chemistry, can participate in various synthetic reactions with retention or cleavage of the strained three‐membered ring. Direct cross‐coupling ring‐opening reaction such molecules access organic compounds, as ketones has great importance medicinal chemistry and material sciences. Hence, coupling reaction/cyclization cyclopropanols for constructing new valuable presence a transition metal catalyst under metal‐free conditions is described this context. The features are discussed, mechanisms challenging highlighted.

Язык: Английский

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Enantioselective Pd- and Cu-Catalyzed Hydrofunctionalization of Methylenecyclopropanes via a Distal C–C Bond Cleavage

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

The enantioselective ring-opening reactions of methylenecyclopropanes (MCPs) involving C–C bond activation via oxidative addition transition metals have been rarely reported. Here, we disclose a Pd/Cu-catalyzed enantio- and regioselective coupling between cyclic imino esters MCPs to produce α-allylated 2H-pyrrole derivatives. In this reaction, azomethine ylide formed by chiral copper catalyst with ketimine ester would serve as nucleophile react activated palladium catalysis. This bimetallic system exhibited broad substrate scope high regio- enantioselectivities.

Язык: Английский

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Pd-catalyzed acylation and allylation of 2-alkynylanilines with 1,2-diphenylcyclopropenones and gem-difluorinated cyclopropanes: a DFT study

Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

We reported the mechanism of Pd-catalyzed 2-alkynylaniline synthesis into indole by acylation and allylation using density functional theory.

Язык: Английский

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Pd-Catalyzed Cross-Coupling of Cyclopropanols with 2-Br-p-Quinone Methides/2-Br-Cinnamate Esters Followed by a 1,6- and 1,4-Conjugate Addition Reaction

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 10, 2025

A novel cascade Pd-catalyzed cross-coupling reaction of cyclopropyl alcohol-derived ketone homoenolate with 2-Br-p-quinone methides and 2-Br-cinnamate esters followed by a 1,6- 1,4-conjugate addition is disclosed. This protocol converts various alcohols into homoenolate, which undergoes C-C bond formation 2-Br p-quinone esters. The salient features this methodology include its operational simplicity, mild conditions, an environmentally benign protocol, high efficiency, good to excellent yields, wide substrate scope.

Язык: Английский

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