Visible‐Light Promoted Intramolecular para‐Cycloadditions on Simple Aromatics

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(12)

Опубликована: Янв. 27, 2023

Abstract Dearomative cycloadditions are a powerful tool to access large chemical space exploiting simple and ubiquitous building blocks. The energetic burden due the loss of aromaticity has however greatly limited their synthetic potential. We devised general intramolecular method that overcomes these limitations thanks photosensitization allenamides. visible‐light‐promoted process gives complex [2.2.2]‐(hetero)‐bicyclooctadienes at room temperature, likely through stabilization transient (bi)radicals by naphthalene. reaction tolerates several valuable functionalities, offering convenient handle for myriad applications, including original isoindoles metal complexes.

Язык: Английский

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Recent advances in cascade reactions and their mechanistic insights: a concise strategy to synthesize complex natural products and organic scaffolds

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(18), С. 3653 - 3674

Опубликована: Янв. 1, 2022

This review features a broad interest in compiling range of cascade transformations under various classifications based on nature and reactivity the main ingredient to solve diverse challenges organic synthesis create fascinating molecules.

Язык: Английский

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Boosting Energy‐Transfer Processes via Dispersion Interactions

Chemistry - A European Journal, Год журнала: 2024, Номер 30(15)

Опубликована: Янв. 15, 2024

Abstract The generation of open‐shell intermediates under mild conditions has opened broad synthetic opportunities during this century. However, these reactive species often require a case specific and tailored tuning experimental parameters in order to efficiently convert substrates into products. We report general approach that can overcome ubiquitous limitations for several visible‐light promoted energy‐transfer processes. use either naphthalene (5–20 equiv.) or simple binaphthyl derivatives (10–30 mol %) greatly increases their efficiency, giving rise new strategy catalysis. trend is consistent among different media, photocatalysts, light sources substrates, allowing one improve existing methods, more easily optimize ones, and, moreover, disclose otherwise inaccessible reaction pathways.

Язык: Английский

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Recent Development of Photoresponsive Liposomes Based on Organic Photosensitizers, Au Nanoparticles, and Azobenzene Derivatives for Nanomedicine

ACS Applied Nano Materials, Год журнала: 2022, Номер 5(10), С. 14171 - 14190

Опубликована: Сен. 27, 2022

Photoresponsive liposomes are controlled-release modified by photoresponsive materials. They use light with high spatial and temporal precision as a means of regulation. After excitation at appropriate wavelengths, can influence the permeability phospholipid bilayers through photothermal or photoisomerization effect The causes layer to become dispersed local heating, modulates release behavior establishing permeation channels on changes in dipole moments azobenzene derivatives. Currently, widely used cutting-edge strategy for nanomedicine. In this paper, three types based organic photosensitizers, Au nanoparticles, derivatives abundant research reports were introduced differences photoresponse principles forms different This review aims reflect structures, properties, materials, action liposomes. Moreover, work outlines current status their application field

Язык: Английский

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Visible-Light-Promoted Tandem Skeletal Rearrangement/Dearomatization of Heteroaryl Enallenes

Molecules, Год журнала: 2024, Номер 29(3), С. 595 - 595

Опубликована: Янв. 25, 2024

Access to complex three-dimensional molecular architectures via dearomatization of ubiquitous aryl rings is a powerful synthetic tool, which faces, however, an inherent challenge overcome energetic costs due the loss aromatic stabilization energy. Photochemical methods that allow one populate high-energy states can thus be ideal strategy accomplish otherwise prohibitive reaction pathways. We present original dearomative rearrangement heteroaryl acryloylallenamides leads fused tricycles. The visible-light-promoted method occurs under mild conditions and tolerates variety functional groups. According DFT modeling used rationalize outcome cascade, involves sequential [2+2] allene-alkene photocycloaddition, followed by selective retro- step paves way for partner. This scenario with respect reported photochemical reactivity similar substrates holds promise ample future developments.

Язык: Английский

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Base-promoted Conia-ene cyclization of propargyl amides

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(36), С. 7311 - 7315

Опубликована: Янв. 1, 2023

We report a tBuOK-promoted synthesis of 1,3-dihydro-2H-pyrrol-2-one and 4-methylenepyrrolidin-2-one systems via Conia-ene like intramolecular cyclization. The method features extremely short reaction times (5 min) mild conditions (rt), enabling the trapping propargyl unit by an amide enolate. An intriguing anionic chain mechanism is at work, which can trigger isomerization exo-alkene giving access to otherwise elusive endo-product.

Язык: Английский

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Progress in Construction of 2H-Pyrrol-2-ones Skeleton

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(1), С. 57 - 57

Опубликована: Янв. 1, 2023

Язык: Английский

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The visible-light-promoted intermolecular para-cycloadditions of allenamides on naphthalene

Tetrahedron Chem, Год журнала: 2023, Номер 8, С. 100053 - 100053

Опубликована: Ноя. 10, 2023

The preparation of bridged bicyclooctadienes through the dearomatization simple arenes is an interesting synthetic tool to access a vast chemical space elegant molecular architectures from wide range and cheap building blocks. However, energetic toll due loss aromatic stabilization has greatly limited development para-cycloadditions, especially with respect intermolecular processes. We report herein first general approach for selective naphthalene. visible-light-promoted reaction occurs under mild conditions over ample substrates it involves initial sensitization acylallenamide. Moreover, complete control on difunctionalization either internal or terminal C–C double bond observed depending substrate functionalization.

Язык: Английский

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Photocatalyst-free, visible-light-induced regio- and stereoselective synthesis of phosphorylated enamines from N-allenamides via [1,3]-sulfonyl shift at room temperature

Chemical Science, Год журнала: 2024, Номер 15(43), С. 17962 - 17970

Опубликована: Янв. 1, 2024

Herein, we report the first visible-light-induced strategy for rapid synthesis of densely functionalized α- and γ-phosphorylated β-sulfonyl enamines in a regio- stereoselective manner from N -sulfonyl allenamides H-phosphine oxides.

Язык: Английский

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Sequential Strategies to Trigger Mild Dearomative Diels–Alder Cyclizations

Organic Letters, Год журнала: 2023, Номер 25(13), С. 2233 - 2237

Опубликована: Март 24, 2023

Dihydronaphthalenes are present in several functional molecules, but their assembly is challenging. However, a sequential strategy can induce the key annullation of an alkyne with vinylarene under mild conditions. Products form good yields, ample tolerance via domino nucleophilic substitution and dearomative Diels-Alder ene reactions. DFT modeling data show that alkali cations crucial to ensure smooth cyclization on situ generated intermediates.

Язык: Английский

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