Rh(III)-Catalyzed Atroposelective C–H Selenylation of 1-Aryl Isoquinolines

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 6009 - 6015

Опубликована: Апрель 5, 2024

Rhodium(III)-catalyzed atroposelective C–H selenylation of 1-aryl isoquinolines has been achieved. The direct reaction between and 2-(phenylselanyl)isoindoline-1,3-dione in the presence chiral SCpRh(III) complex afforded a series axially isoquinoline selenides up to 95% yield 96% ee. features mild conditions broad substrate scope. DFT calculations revealed that C–Se bond formation step proceeds through formal SN2 pathway.

Язык: Английский

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Catalytic Enantioselective Aminative Difunctionalization of Alkenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 7029 - 7038

Опубликована: Март 1, 2024

Enantioselective difunctionalization of alkenes offers a straightforward means for the rapid construction enantioenriched complex molecules. Despite tremendous efforts devoted to this field, enantioselective aminative remains challenge, particularly through an electrophilic addition fashion. Herein, we report unprecedented approach via copper-catalyzed with external azo compounds as nitrogen sources. A series valuable cyclic hydrazine derivatives either [3 + 2] cycloaddition or intramolecular cyclization have been achieved in high chemo-, regio-, enantio-, and diastereoselectivities. In transformation, wide range functional groups, such carboxylic acid, hydroxy, amide, sulfonamide, aryl could serve nucleophiles. Importantly, new cyano oxazoline chiral ligand was found play crucial role control enantioselectivity.

Язык: Английский

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Controlling the regioselectivity of the bromolactonization reaction in HFIP

Chemical Science, Год журнала: 2024, Номер 15(19), С. 7187 - 7197

Опубликована: Янв. 1, 2024

The halolactonization reaction provides rapid access to densely functionalized lactones from unsaturated carboxylic acids. endo/exo regioselectivity of this cyclization is primarily determined by the electronic stabilization alkene substituents, thus making it inherently dependent on substrate structures. Therefore method often affords one type halolactone regioisomer only. Herein, we introduce a simple and efficient for regioselectivity-switchable bromolactonization reactions mediated HFIP solvent. Two sets conditions were developed, each forming endo-products or exo-products in excellent regioselectivity. A combination computational experimental mechanistic studies not only confirmed crucial role HFIP, but also revealed formation under kinetic control thermodynamic control. This study paves way future work use perfluorinated solvents dictate outcomes organic synthesis.

Язык: Английский

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Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Green Chemistry, Год журнала: 2024, Номер 26(4), С. 1846 - 1875

Опубликована: Янв. 1, 2024

Organocatalytic enantioselective cross-dehydrogenative coupling reaction provides a great opportunity for the synthesis of highly enantioenriched molecules. In this review, recent progress in field is summarized.

Язык: Английский

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Recent progress in the organoselenium-catalyzed difunctionalization of alkenes

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Selenium-based catalysts have recently been utilized to facilitate a variety of new organic transformations, owing their intrinsic advantages, including low cost, toxicity, stability in both air and water, strong compatibility with diverse functional groups. The difunctionalization alkenes-the process incorporating two groups onto carbon-carbon double bond-has garnered particular interest within the chemical community its significant applications synthesis. Recently, organoselenium-catalyzed alkenes has emerged as an ideal powerful route obtain high-value vicinal difunctionalized molecules. This review emphasizes recent advancements this rapidly evolving field, focusing on scope, limitations, mechanisms various reactions.

Язык: Английский

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Organocatalytic Atroposelective Hydroselenation of Alkynes To Access Axially Chiral Vinyl Selenides

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4051 - 4060

Опубликована: Фев. 20, 2025

Язык: Английский

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Rhodium-Catalyzed Asymmetric Hydroselenation of 1-Alkynylindoles for Atroposelective Synthesis of Vinyl Selenoethers

ACS Catalysis, Год журнала: 2024, Номер 14(17), С. 13055 - 13064

Опубликована: Авг. 15, 2024

Catalytic asymmetric hydrofunctionalization of π-bonds has been extensively studied, but the alkynes that affords atropoisometric products remains heavily underexplored. We herein report [Rh(COD)OAc]2/Mg(NTf2)2-catayzed highly atroposelective hydroselenation two classes 1-alkynylindoles using selenophenols, where Mg(II) salt both activates Rh catalyst and provides a key NTf2 anion essential for catalytic activity enantioselectivity, affording C–N axially chiral trisubstituted olefins bear relatively low racemization barrier (ΔG‡ ∼ 27 kcal/mol). The system features high activity, mild reaction conditions, good functional group tolerance, regio-, (E)-, enantioselectivity. selenoether moiety in product framework can be readily functionalized to give synthetically useful products.

Язык: Английский

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A Theoretical Study on the Mechanism of Bifunctional Brønsted Acid/Base-Catalyzed CO₂-Fixation Reaction with Homoallylic Amine

The Journal of Organic Chemistry, Год журнала: 2025, Номер 90(6), С. 2172 - 2179

Опубликована: Янв. 31, 2025

The reaction mechanism and the enantioselectivity of Brønsted acid/base (trans-stilbene diamine, simplified by BAM)-catalyzed CO2 fixation with homoallylic amine have been investigated using density functional theory (DFT) calculations. proposed involves initial activation acid, followed nucleophilic attack on to form a carbamate intermediate. base subsequently deprotonates intermediate cyclic product, regenerating acid catalyst. C-O cyclization is enantio-determining step. hydrogen bond network formed catalyst substrate, similar an enzyme pocket, plays key role in stereoselectivity. In addition, energy decomposition analysis (EDA) confirms that bonding driven orbital electrostatic attractions. more basic BAM (OMe at quinoline 7-position) exhibits enhanced enantioselectivity.

Язык: Английский

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Catalytic Enantioselective Friedel–Crafts Reactions of Arenes Enabled by Iranium/Irenium-Ion-Triggered Electrophilic Functionalization

Synlett, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

Abstract The catalytic asymmetric Friedel–Crafts reactions of (hetero)arenes represent a cornerstone in synthetic chemistry due to their ability efficiently incorporate aromatic rings into complex molecular architectures. This account presents comprehensive overview recent advancements the enantioselective (hetero)arenes, with particular focus on that facilitate introduction multiple C–C bonds via iranium/irenium-ion-triggered electrophilic processes. We examine detail strategies and methodologies employed achieve stereoselective incorporation unsaturated bonds, highlighting construction diverse structural scaffolds. Additionally, this showcases broad range applications powerful transformation organic synthesis. 1 Introduction 2 Catalytic Enantioselective Reactions Thiiranium/Thiirenium Ions 2.1 Arylthiiranium/Arylthiirenium-Ion-Triggered 2.2 Trifluoromethylthiiranium/Trifluoromethylthiirenium-Ion-Triggered 3 Haliranium 3.1 Chloriranium-Ion-Triggered 3.2 Bromiranium-Ion-Triggered 3.3 Iodiranium-Ion-Triggered Asymmetric Oxidative Arylation Alkenes 4 Conclusion Outlook

Язык: Английский

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Catalytic Enantioselective Chlorofunctionalizations of N-Substituted Amides Using In Situ Generated HOCl as Hydrogen Bond Source

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

Опубликована: Апрель 29, 2025

Asymmetric organocatalytic halocyclization represents a powerful method for the synthesis of valuable chiral haloheterocycles. However, its heavy dependence on substrates that contain hydrogen bond donors enantiocontrol limits broader application. Here we report catalytic asymmetric chlorofunctionalization olefinic amides do not bear donors, allowing efficient production chlorooxazolidin-2-ones and chloroamino esters featuring quaternary stereocenters, achieved with high yields excellent enantioselectivity. This protocol facilitates N-aryloxazolidin-2-ones establishes useful framework synthesizing antibiotic analogues. Mechanistic studies indicate trace amounts water interact chlorinating agent to produce HOCl in situ, which acts as both proton donor hypochlorite source, thereby promoting cyclization process. strategy significantly broadens potential development diverse array functional molecules.

Язык: Английский

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