Enantioselective para‐C(sp²)−H Functionalization of Alkyl Benzene Derivatives via Cooperative Catalysis of Gold/Chiral Brønsted Acid**

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(40)

Опубликована: Авг. 4, 2022

Abstract An asymmetric para‐ C(sp 2 )−H bond functionalization of alkyl benzene derivatives was successfully developed via cooperative catalysis gold and chiral phosphoric acid (CPA), leading to synthetically useful 1,1‐diaryl motifs. Chiral acid, ligand, molecular sieves were found be crucial for enantioselectivity control this transformation. The salient features protocol include mild conditions, high efficiency, commercially available starting materials, highly chemo‐ site‐ as well enantioselective aromatic C−H functionalization, broad substrate scope, extensive applications the products. mechanistic studies suggested that two CPAs might involved in induction.

Язык: Английский

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Tunable Regiodivergent Reactivity of N-Allenamides with Silacyclobutanes via Palladium Catalysis in the Synthesis of Silacyclic β-Aminosilanes

ACS Catalysis, Год журнала: 2024, Номер 14(14), С. 10882 - 10892

Опубликована: Июль 4, 2024

The key structure of β-aminosilanes has attracted significant interest because their latent biological activities in the field medicinal chemistry. However, structural variety been significantly constrained by absence a comprehensive synthetic approach. Thus, development regiodivergent catalytic systems for construction structurally diverse via an intermolecular cycloaddition strategy would represent addition to limited toolkit available synthesis. We herein present attractive approach synthesis through regioselective N-allenamides with expansion silacyclobutanes catalyzed Pd/PR3. Just selecting suitable protecting group N-allenamides, regioselectivity is completely switched efficiently provide two regioisomers silacyclic β-aminosilanes. Two regioselectivities were proceeded during migratory insertion and reductive elimination process, origin which could be well rationalized using density functional theory calculations.

Язык: Английский

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Rh(III)-Catalyzed Spiroannulation Reaction of N-Aryl Nitrones with 2-Diazo-1,3-indandiones: Synthesis of Spirocyclic Indole-N-oxides and Their 1,3-Dipolar Cycloaddition with Maleimides

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(6), С. 3845 - 3858

Опубликована: Март 8, 2023

An efficient strategy for the preparation of spirocyclic indole-N-oxide compounds through a Rh(III)-catalyzed [4 + 1] spiroannulation reaction N-aryl nitrones with 2-diazo-1,3-indandiones as C1 synthons under extremely mild conditions is presented. From this reaction, 40 indole-N-oxides were easily obtained in up to 98% yield. In addition, title could be successfully used construction structurally intriguing maleimide-containing fused polycyclic scaffolds via diastereoselective 1,3-dipolar cycloaddition maleimides.

Язык: Английский

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Construction of C–N and C–O bonds based on N-allenamide functionalization

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(46), С. 9069 - 9084

Опубликована: Янв. 1, 2022

The review covers recent advances in the development of new methods involving amination and alkoxylation reactions on N -allenamides covering cycloaddition, carbofunctionalization, halogenofunctionalization as well hydrofunctionalization reactions.

Язык: Английский

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Catalytic asymmetric de novo construction of 4-pyrrolin-2-ones via intermolecular formal [3+2] cycloaddition of azoalkenes with azlactones

Chemical Communications, Год журнала: 2023, Номер 59(39), С. 5902 - 5905

Опубликована: Янв. 1, 2023

The chiral phosphoric acid-catalyzed asymmetric intermolecular formal [3+2] cycloaddition of azoalkenes with azlactones has been established. This convergent protocol leads to a facile and enantioselective de novo construction wide range fully substituted 4-pyrrolin-2-ones bearing carbon atom in good yields excellent enantioselectivities (26 examples, 72-95% 87-99% ee).

Язык: Английский

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Zinc-catalyzed asymmetric [3 + 2] annulations for the construction of chiral spiro[1-indanone-γ-butyrolactones] via a C–N bond cleavage process

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(21), С. 5819 - 5824

Опубликована: Янв. 1, 2022

This is an efficient asymmetric Michael/lactonization cascade reaction via a Brønsted base and Lewis acid cooperative activation model.

Язык: Английский

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Chiral-Boron-Complex-Catalyzed Asymmetric [3 + 2] Cycloaddition of 2′-Hydroxychalcones with N,N′-Cyclic Azomethine Imines

Organic Letters, Год журнала: 2022, Номер 24(35), С. 6449 - 6454

Опубликована: Авг. 30, 2022

We report the (R)-3,3'-I2-BINOL-boron-complex-catalyzed asymmetric 1,3-dipolar cycloaddition of 2'-hydroxychalcones with N,N'-cyclic azomethine imines, providing corresponding N,N'-bicyclic pyrazolidine derivatives three contiguous tertiary stereocenters in high yields excellent diastereo- and enantioselectivities (up to >99:1 diastereomeric ratio >99% enantiomeric excess). This catalytic system exhibits advantages mild reaction conditions, efficiency, broad substrate scopes.

Язык: Английский

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Palladium-Catalyzed Asymmetric [3＋4] Cycloadditions for the Construction of Cyclohepta[b]indoles

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(8), С. 2864 - 2864

Опубликована: Янв. 1, 2023

A Pd-catalyzed decarboxylation strategy for the efficient synthesis of cyclohepta [b]indoles in good yields with to excellent enantioselectivities and moderate diastereoselectivities is reported.In this procedure, viny indoloxazolidones were activated by Pd catalyst generate zwitterionic intermediates situ, which then trapped electro-deficient diene species via asymmetric [3＋4] cycloaddition process.

Язык: Английский

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Gold-Catalyzed Regio- and Stereoselective Alkenylation of Quinoline N-Oxides with Allenamides

Organic Letters, Год журнала: 2024, Номер 26(26), С. 5493 - 5499

Опубликована: Июнь 21, 2024

A gold-catalyzed cycloaddition/ring opening of allenamides with quinoline N-oxides has been developed, which provides C2-alkenylated quinolines high E selectivity in moderate to yields. It is noted that a C8 or C7 substituent are crucial for this catalytic reaction.

Язык: Английский

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Metal‐free Reaction of Allenamides with In‐Situ Formed Trifluoromethylnitrones as a Route to Highly Functionalized Isoxazolidines

Asian Journal of Organic Chemistry, Год журнала: 2023, Номер 12(10)

Опубликована: Авг. 21, 2023

Abstract An additive‐free three‐component reaction of allenamides with in situ generated trifluoromethylnitrones has been uncovered. The afforded an interesting class trifluoromethylated methyleneisoxazolidines under mild conditions. Additionally, a gram‐scale and the reductive transformation isoxazolidines to aminomethylated allyl alcohol illustrate high synthetic utility present strategy.

Язык: Английский

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