Dual Ni/photoredox-catalyzed asymmetric cross-coupling to access chiral benzylic boronic esters

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

Опубликована: Март 12, 2021

Abstract The flourishing Ni/photoredox-catalyzed asymmetric couplings typically rely on redox-neutral reactions. In this work, we report a reductive cross-coupling of aryl iodides and α-chloroboranes under dual catalytic regime to further enrich the metallaphotoredox chemistry. This approach proceeds mild conditions (visible light, ambient temperature, no strong base) access versatile benzylic boronic esters with good functional group tolerance excellent enantioselectivities.

Язык: Английский

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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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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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Ir‐Catalyzed Enantioselective Synthesis of gem‐Diborylalkenes Enabled by 1,2‐Boron Shift

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(32)

Опубликована: Июнь 15, 2023

Abstract Asymmetric cross‐couplings based on 1,2‐carbon migration from B‐ate complexes have been developed efficiently to access valuable organoboronates. However, enantioselective reactions triggered by 1,2‐boron shift remained be unaddressed synthetic challenge. Here, Ir‐catalyzed asymmetric allylic alkylation enabled was developed. In this reaction, we disclosed that excellent enantioselectivities were achieved through an interesting dynamic kinetic resolution (DKR) process of carbonates at the elevated temperature. Notably, highly (bis‐boryl)alkenes array diversifications versatile molecules. Extensive experimental and computational studies conducted elucidate reaction mechanism DKR clarify origin enantioselectivities.

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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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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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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Nickel‐Catalyzed Arylboration of Alkenylarenes: Synthesis of Boron‐Substituted Quaternary Carbons and Regiodivergent Reactions

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(32), С. 10956 - 10960

Опубликована: Июнь 28, 2019

A method for the construction of boron-substituted quaternary carbons or diarylquaternary by arylboration highly substituted alkenylarenes is presented. wide range alkenes and arylbromides can participate in this reaction thus allowing a diverse assortment products to be prepared. In addition, solvent dependent regiodivergent 1,2-disubstituted presented, greatly increasing scope that accessed.

Язык: Английский

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Organoselenium small molecules as catalysts for the oxidative functionalization of organic molecules

New Journal of Chemistry, Год журнала: 2019, Номер 43(23), С. 8852 - 8864

Опубликована: Янв. 1, 2019

This perspective highlights the critical analysis of challenges, in past decade, which led to development organoselenium compounds and their use as versatile catalysts organic synthesis towards oxidation olefins C–H bonds. Furthermore, emphasis here differs from previous reviews field by classifying various types catalyses diverse strategies.

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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