Catalytic, Enantioselective Sulfenofunctionalization of Alkenes: Development and Recent Advances

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(45), С. 19796 - 19819

Опубликована: Май 26, 2020

The last decade has witnessed a burgeoning of new methods for the enantioselective vicinal difunctionalization alkenes initiated by electrophilic sulfenyl group transfer. addition sulfenium ions to results in generation chiral, non-racemic thiiranium ions. These highly reactive intermediates are susceptible attack myriad nucleophiles stereospecific ring-opening event afford anti 1,2-sulfenofunctionalized products. practical application ion transfer been enabled advances field Lewis base catalysis. This Review will chronicle initial discovery and characterization followed determination their configurational stability challenges developing variants. Once framework reactivity established, critical analysis pioneering studies be presented. Finally, comprehensive discussion modern synthetic applications categorized around type nucleophile employed sulfenofunctionalization.

Язык: Английский

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Oxoammonium salts are catalysing efficient and selective halogenation of olefins, alkynes and aromatics

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Июнь 23, 2021

Abstract Electrophilic halogenation reactions have been a reliable approach to accessing organohalides. During the past decades, various catalytic systems developed for activation of haleniums. However, there is still short effective catalysts, which could cover and broad scope unsaturated compounds. Herein, TEMPO (2,2,6,6-tetramethylpiperidine nitroxide) its derivatives are disclosed as active catalysts electrophilic olefins, alkynes, aromatics. These stable, readily available, reactive enough activate haleniums including Br + , I even Cl reagents. This system applicable halogenations haloarylation olefins or dibromination were rarely realized in previous Lewis base catalysis acid catalysis. The high ability attributed synergistic model halogenating reagents, where carbonyl group halogen atom both activated by present

Язык: Английский

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Chiral Selenide/Achiral Sulfonic Acid Cocatalyzed Atroposelective Sulfenylation of Biaryl Phenols via a Desymmetrization/Kinetic Resolution Sequence

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(7), С. 2943 - 2952

Опубликована: Фев. 10, 2022

Enantioselective synthesis of axially chiral sulfur-containing biaryl derivatives through the electrophilic sulfenylation phenols has been achieved for first time. This catalytic asymmetric system, which involves sequential desymmetrization and kinetic resolution, is enabled by a combination novel 3,3'-disubstituted BINOL-derived selenide catalyst an achiral sulfonic acid. Control experiments computational studies suggest that multiple noncovalent interactions between cocatalysts substrate, especially network hydrogen bond interactions, play crucial role in determining enantioselectivity reactivity.

Язык: Английский

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Recent advances in thiolation via sulfur electrophiles

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(23), С. 6684 - 6707

Опубликована: Янв. 1, 2022

This review systematically summarizes the recent developments for constructing sulfur compounds from electrophiles, and mechanism mainly involved thirranium ions, ylides, C–S cross coupling electrophilic substitution.

Язык: Английский

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Chalcogen bonding catalysis

Chemical Society Reviews, Год журнала: 2023, Номер 53(2), С. 586 - 605

Опубликована: Дек. 7, 2023

Catalysts play a major role in chemical synthesis, and catalysis is considered to be green economic process. Catalysis dominated by covalent interactions between the catalyst substrate. The design of non-covalent catalysts came into limelight only recently. Hydrogen bonding (HB) are well established among catalysts, including asymmetric HB catalysts. Though halogen (XB) its version gaining admiration, chalcogen (ChB) budding stage. This tutorial review will focus on recently evolved emphasis given chiral molecules. Since successful enantioselective yet reported, this basics catalysis, chalcogenide rigidification transition states ChB, stabilization cations chalcogens, details unsuccessful enantioseparation racemic molecules using existence ChB biomolecules.

Язык: Английский

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Difunctionalization Processes Enabled by Hexafluoroisopropanol

ACS Organic & Inorganic Au, Год журнала: 2024, Номер 4(3), С. 287 - 300

Опубликована: Март 4, 2024

In the past 5 years, hexafluoroisopropanol (HFIP) has been used as a unique solvent or additive to enable challenging transformations through substrate activation and stabilization of reactive intermediates. this Review, we aim at describing difunctionalization processes which were unlocked when HFIP was involved. Specifically, focus on cyclizations additions alkenes, alkynes, epoxides, carbonyls that introduce wide range functional groups interest.

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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Selenium-π-Acid Catalyzed Oxidative Functionalization of Alkynes: Facile Access to Ynones and Multisubstituted Oxazoles

ACS Catalysis, Год журнала: 2018, Номер 8(7), С. 6745 - 6750

Опубликована: Июнь 19, 2018

Unprecedented selenium-catalyzed propargylic oxidation of alkynes is disclosed. Various propargylphosphonates and 3-alkynoates were efficiently converted to valuable ynones via unusual C–C triple bond migration deselenenylation at a vinyl carbon. By the strategies tautomerization enamine intermediate SN2 displacement, similar conditions effective for oxidative difunctionalization ynamides afford multisubstituted oxazoles with high regioselectivity. Mechanistic studies revealed these detailed processes.

Язык: Английский

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Lewis Base/Brønsted Acid Co‐catalyzed Enantioselective Sulfenylation/Semipinacol Rearrangement of Di‐ and Trisubstituted Allylic Alcohols

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(36), С. 12491 - 12496

Опубликована: Июль 11, 2019

An enantioselective sulfenylation/semipinacol rearrangement of 1,1-disubstituted and trisubstituted allylic alcohols was accomplished with a chiral Lewis base Brønsted acid as cocatalysts, generating various β-arylthio ketones bearing an all-carbon quaternary center in moderate to excellent yields enantioselectivities. These arylthio ketone products are common intermediates many applications, for example, the design new catalysts/ligands total synthesis natural products. Computational studies (DFT calculations) were carried out explain enantioselectivity role acid. Additionally, synthetic utility this method exemplified by (-)-herbertene one-pot sulfoxide sulfone.

Язык: Английский

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Enantioselective, Lewis Base-Catalyzed, Intermolecular Sulfenoamination of Alkenes

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(35), С. 13767 - 13771

Опубликована: Авг. 21, 2019

A method for the catalytic, enantioselective, intermolecular, 1,2-sulfenoamination of alkenes is described. Functionalization achieved through intermediacy an enantioenriched, configurationally stable thiiranium ion generated by Lewis base activation a readily available sulfur electrophile. diverse set anilines and benzylamines react with different styrenes to afford products in good yield stereoselectivity. Downstream manipulation facilitated deprotonation amines enable carbon–sulfur bond cleavage.

Язык: Английский

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