Substrate-controlled [4+1] and [3+2] annulations of ninhydrin-derived Morita–Baylis–Hillman carbonates to access polysubstituted furans and cyclopentenes

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(27), P. 3717 - 3720

Published: Jan. 1, 2024

The substrate-enabled switching of the regioselectivity allows for efficient regiocontrol via [4+1] and [3+2] annulations ninhydrin-derived MBH carbonates with α,β-unsaturated ketones to access highly substituted furans cyclopentene.

Language: Английский

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Cooperative Gold(I)/DMAP Catalysis Enabled (2 + 3) Cycloadditions of Yne–Enones with Oxindole-Derived MBH Carbonates

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3790 - 3795

Published: April 26, 2024

A cooperative gold(I)/DMAP system catalyzes the (2 + 3) cycloadditions of yne-enones with oxindole-derived Morita-Baylis-Hillman (MBH) carbonates, yielding diverse bispiro-cyclopentene oxindole products. The mild, scalable protocol demonstrates broad substrate scope and excellent chemo- diastereoselectivity. Mechanistic study reveals pivotal roles both catalysts in unique cycloaddition. This strategy showcases superiority achieving transformation chemoselectivity diastereoselectivity, unattainable through traditional monocatalytic methodologies.

Language: Английский

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Asymmetric palladium-catalyzed decarboxylative [3 + 2] cycloaddition: straightforward construction of chiral spiro-heterocyclic scaffolds

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(5), P. 1479 - 1483

Published: Jan. 1, 2024

We developed an asymmetric Pd-catalyzed [3 + 2] cycloaddition of α,β-unsaturated pyrazolones with vinylethylene carbonates. An array spiro-tetrahydrofuran-pyrazolones were obtained in high yields excellent enantioselectivities.

Language: Английский

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Construction of 3,4-Dihydroquinolone Derivatives through Pd-Catalyzed [4+2] Cycloaddition of Vinyl Benzoxazinanones with α-Alkylidene Succinimides

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3279 - 3291

Published: Feb. 20, 2024

The construction of 3,4-dihydroquinolone derivatives has attracted a considerable amount attention due to their extensive applications in medicinal chemistry. In this study, we present the Pd-catalyzed [4+2] cycloaddition vinyl benzoxazinanones with α-alkylidene succinimides for efficient synthesis 3,4-dihydroquinolones. This approach presents numerous advantages, including ready availability starting materials, mild reaction conditions without use additional bases, and wide range substrates. particular, all desired products can be easily afforded high yields (≤99%) excellent diastereoselectivities (>20:1). practicality reliability strategy were demonstrated by successful scale-up subsequent straightforward synthetic transformations.

Language: Английский

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Catalyst-controlled regiodivergence and stereodivergence in formal cross-[4+2] cycloadditions: The unique effect of bismuth(III)

Science Advances, Journal Year: 2025, Volume and Issue: 11(13)

Published: March 26, 2025

The [4+2] cycloaddition is crucial for constructing six-membered rings in pharmaceuticals and natural products. Cross-[4+2] cycloadditions offer greater product diversity than traditional diene-dienophile reactions due to multiple possible pathways. However, precise control over regio- stereoselectivity various isomers remains a great challenge. This study reports catalyst-controlled regiodivergent formal cross-cycloadditions of acyclic dienes enones, significantly enhancing access diverse pyrazole-fused spirooxindoles. Chiral phosphoric acid (CPA) catalysis enables endoselective cycloadditions, while Bi(III) with CPA ligand yields [2+4] products high stereoselectivity. A Claisen rearrangement the adduct produces exo-selective product, further increasing stereochemical enabling synthesis six stereo-isomers from single substrate set. DFT calculations reveal that reverses regioselectivity by repositioning reactants pocket stabilizing enone oxygen’s negative charge. In addition, 3as demonstrates therapeutic potential against triple-negative breast cancer, an IC 50 8.5 μM MDA-MB-453 cells.

Language: Английский

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Visible-light-induced C–S bond formation of pyrazolin-5-ones with thioureas to pyrazol-4-yl carbamimidothioates

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 580, P. 115086 - 115086

Published: April 8, 2025

Language: Английский

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Lewis Base Controlled (4 + 3) and (4 + 2) Annulations of MBH Carbonates with Benzofuran‐derived Azadienes: Access to Highly Substituted Benzofuro[3,2‐b]azepines and Spirotetrahydroquinolines

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(21), P. 4521 - 4527

Published: Aug. 7, 2024

Abstract Catalyst‐controlled switchable (4+3) and (4+2) annulation reactions of Morita–Baylis–Hillman carbonates with benzofuran‐derived azadienes have been established. Employing PCy 3 as the catalyst, reaction could provide a variety synthetically useful benzofuro[3,2‐ b ]azepines in good yields (80–92%) excellent chemo‐ regioselectivities via cycloaddition reactions. Whereas changing catalyst from to DMAP, were switched construct highly substituted spirotetrahydroquinoline scaffolds three sequential stereocenters containing all‐carbon spiro‐quaternary efficiency diastereoselectivities (92–96% all cases>25:1 dr ) annulations. In addition, synthetic utility this method was further showcased by gram‐scale transformations product.

Language: Английский

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DMAP Catalyzed Ring-Opening/Cycloaddition of Vinyl Oxiranes with Activated Ketone Compounds to Construct the 1,3-Dioxolane Skeletons

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9322 - 9327

Published: Oct. 24, 2024

The present work develops a DMAP-catalyzed [3 + 2] cycloaddition of vinyl oxiranes with activated ketone compounds, affording dioxolane derivatives moderate to excellent yields. This approach represents the first Lewis base (LB)-catalyzed ring-opening reaction epoxides, simultaneously providing rare oxygen-containing active intermediate in this field. gram-scale preparation and facile derivatization cycloadduct highlight significant synthetic potential strategy.

Language: Английский

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Synthesis of functionalized spiro[indanone-benzazepine] scaffolds via [4 + 3] annulation reaction of N-(o-chloromethyl)aryl amides with ninhydrin-derived Morita−Baylis−Hillman carbonates

Tetrahedron, Journal Year: 2023, Volume and Issue: 150, P. 133772 - 133772

Published: Dec. 1, 2023

Language: Английский

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Chemoselective synthesis of bridged benzo[no]tetraphen-8-one via copper-catalyzed radical dimerization of 1-alkynylnaphthols

Tetrahedron Letters, Journal Year: 2024, Volume and Issue: 136, P. 154929 - 154929

Published: Jan. 26, 2024

Language: Английский

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