Enantioselective Synthesis of Planar‐Chiral Sulfur‐Containing Cyclophanes by Chiral Sulfide Catalyzed Electrophilic Sulfenylation of Arenes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(10)

Опубликована: Янв. 17, 2024

Abstract An efficient catalytic asymmetric electrophilic sulfenylation reaction for the synthesis of planar‐chiral sulfur‐containing cyclophanes has been developed first time. This was achieved by using a new Lewis base catalyst and ortho ‐trifluoromethyl‐substituted sulfenylating reagent. Using substrates with low rotational energy barrier, transformation proceeded through dynamic kinetic resolution, high barrier allowed to undergo resolution process. Meanwhile, this compatible desymmetrization process when symmetric were used. Various readily obtained in moderate excellent yields enantioselectivities (up 97 % yield 95 ee). approach used synthesize pharmaceutically relevant molecules. Density functional theory calculations showed that π‐π interactions between sulfenyl group aromatic ring substrate play crucial role enantioinduction reaction.

Язык: Английский

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Electrophilic Selenium-Catalyzed Desymmetrizing Cyclization to Access P-Stereogenic Heterocycles

ACS Catalysis, Год журнала: 2023, Номер 13(20), С. 13301 - 13309

Опубликована: Окт. 2, 2023

The construction of phosphorus stereocenters under metal-free conditions remains a formidable challenge. Herein, we report mechanistically distinct chiral electrophilic selenium catalysis-enabled desymmetrizing cyclization to access valuable phosphorus-stereogenic heterocycles with high efficiency. This ambient temperature method affords broad range compounds that bear phenolic hydroxyl group as useful synthetic handle and, thus, enriches the toolbox for rapid generation molecular complexity. control experiments and DFT calculations indicate dual-hydrogen-bonding bridge formed between substrate TfO– anion plays crucial role in determining enantioselectivity transformation.

Язык: Английский

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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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An electrocatalytic mono-functionalization of alkenes towards alkenyl selenium sulfonates

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

In this study, a straightforward and environmentally benign electrochemical mono-functionalization of alkenes has been established for the synthesis alkenyl selenium sulfonates using elemental as source.

Язык: Английский

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Catalytic asymmetric synthesis of sulfur-containing atropisomers by C-S bond formations

Science China Chemistry, Год журнала: 2023, Номер 66(12), С. 3331 - 3346

Опубликована: Ноя. 17, 2023

Язык: Английский

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Lewis Base Catalyzed Selenofunctionalization of Alkynes with Acid‐Controlled Divergent Chemoselectivity^†

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(14), С. 1623 - 1629

Опубликована: Март 15, 2024

Comprehensive Summary Lewis base catalyzed and Brønsted acid controlled chemodivergent electrophilic selenofunctionalizations of alkynes were developed for the first time. Various selenium‐containing tetrasubstituted alkenes readily obtained in moderate to excellent yields with complete E / Z selectivities. As substrates 1‐ethynyl naphthol derivatives, linear produced via intermolecular oxygen nucleophilic attack absence additive; contrast, cyclic generated through intramolecular carbon capture addition acid.

Язык: Английский

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Catalytic Asymmetric Cyclizative Rearrangement of Anilines and Vicinal Diketones to Access 2,2‐Disubstituted Indolin‐3‐ones

Advanced Science, Год журнала: 2024, Номер 11(25)

Опубликована: Апрель 24, 2024

Abstract The efficient synthesis of chiral 2,2‐disubstituted indolin‐3‐ones is great importance due to its significant synthetic and biological applications. However, catalytic enantioselective methods for de novo such heterocycles remain scarce. Herein, a novel cyclizative rearrangement readily available anilines vicinal diketones the one‐step construction enantioenriched presented. reaction proceeds through self‐sorted [3+2] heteroannulation/regioselective dehydration/1,2‐ester shift process. Only phosphoric acid employed promote entire sequence simplify manipulation this protocol. Various common aniline derivatives are successfully applied asymmetric as 1,3‐binuclephiles first time. Remarkably, observed stereoselectivity proposed originate from an amine‐directed regio‐ ortho ‐Csp 2 ‐H addition ketones. A range transformations resulting products demonstrated well.

Язык: Английский

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Recent Advances in Catalytic Desymmetrization for the Synthesis of Axially Chiral Biaryls

ChemCatChem, Год журнала: 2024, Номер unknown

Опубликована: Июнь 7, 2024

Abstract Atropisomeric compounds have been discovered in pharmaceuticals and materials science, their enantioselective syntheses gained tremendous attention. Among strategies for catalytic atroposelective synthesis, desymmetrization provides robust straightforward approaches to axially chiral biaryls. Due the relative ease of substrate design compared other strategies, has emerged as a pivotal stage converting fascinating chemistry into its counterpart, despite challenges such formation achiral products by subsequent reactions long distance between reaction site stereogenic axis. This review offers comprehensive overview recent advancements using organo‐ metal catalysts, addressing solutions, aims provide insights future developments this field.

Язык: Английский

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Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 15, 2024

Inherently chiral calixarenes hold great potential for applications in recognition, sensing, and asymmetric catalysis due to their unique structures. However, special structures relatively large sizes, the catalytic synthesis of inherently is challenging with very limited examples available. Here, we present an efficient method enantioselective sulfur-containing calix[4]arenes through desymmetrizing electrophilic sulfenylation calix[4]arenes. This reaction enabled by a 1,1'-binaphthyl-2,2'-diamine-derived sulfide catalyst hexafluoroisopropanol. Various are obtained moderate excellent yields high enantioselectivities. Control experiments indicate that thermodynamically favored C-SAr product formed from kinetically N-SAr combination hexafluoroisopropanol crucially important both enantioselectivity reactivity. Due authors report

Язык: Английский

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Copper(I)-Catalyzed Asymmetric α-Selenenylation of 2-Acylimidazoles

JACS Au, Год журнала: 2025, Номер 5(2), С. 578 - 585

Опубликована: Янв. 21, 2025

A general method for the catalytic asymmetric α-selenenylation of simple carbonyl compounds is lacking. Herein, a copper(I)-catalyzed enantioselective 2-acylimidazoles with electrophilic selenosulfonates uncovered. The reaction enjoys advantages mild conditions, easy protocol, and broad substrate scopes on both selenosulfonates. Mechanistic studies reveal pincer Cu(I)-(S,S)-Ph-BOPA complex as active catalyst. Some traditional selenenylation reagents, such PhSeCl, PhSeSePh, 2-(phenylselanyl)isoindoline-1,3-dione lead to inferior results in terms yield enantioselectivity, highlighting superiority Finally, several transformations based 2-acylimidazole group selenoether are successfully carried out, demonstrating synthetic utilities present methodology.

Язык: Английский

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