Enantioselective electrochemical cobalt-catalyzed aryl C–H activation reactions

Science, Год журнала: 2023, Номер 379(6636), С. 1036 - 1042

Опубликована: Март 10, 2023

Enantioselective redox transformations typically rely on costly transition metals as catalysts and often stoichiometric amounts of chemical agents well. Electrocatalysis represents a more sustainable alternative, in particular through the use hydrogen evolution reaction (HER) place oxidant. In this work, we describe strategies for HER-coupled enantioselective aryl carbon-hydrogen bond (C-H) activation reactions using cobalt precious metal catalyst asymmetric oxidation. Thus, highly nitrogen-hydrogen (C-H N-H) annulations carboxylic amides were achieved, which gave access to point axially chiral compounds. Furthermore, cobalt-mediated electrocatalysis enabled preparation various phosphorus (P)-stereogenic compounds by selective desymmetrization dehydrogenative C-H reactions.

Язык: Английский

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Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Год журнала: 2023, Номер 123(16), С. 10079 - 10134

Опубликована: Авг. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Язык: Английский

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Enantio‐ and Regioselective Electrooxidative Cobalt‐Catalyzed C−H/N−H Annulation with Alkenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(11)

Опубликована: Янв. 20, 2023

In recent years, the merging of electrosynthesis with 3d metal catalyzed C-H activation has emerged as a sustainable and powerful technique in organic synthesis. Despite impressive advantages, development an enantioselective version remains elusive poses daunting challenge. Herein, we report first electrooxidative cobalt-catalyzed enantio- regioselective C-H/N-H annulation olefins using undivided cell at room temperature (up to 99 % ee). t Bu-Salox, rationally designed Salox ligand bearing bulky tert-butyl group ortho-position phenol, was found be crucial for this asymmetric reaction. A strong cooperative effect between Bu-Salox 3,4,5-trichloropyridine enabled highly more challenging α-olefins without secondary bond interactions 96 ee 97 : 3 rr). Cyclovoltametric studies, preparation, characterization, transformation cobaltacycle intermediates shed light on mechanism

Язык: Английский

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Base‐Promoted Electrochemical Co^II‐catalyzed Enantioselective C−H Oxygenation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(21)

Опубликована: Март 20, 2023

Metalla-electrocatalyzed C-H oxygenation represents one of the most straightforward and sustainable approaches to access valuable oxygenated molecules. Despite significant advances, development enantioselective electrochemical reaction is very challenging remains elusive. Herein, we described first CoII -catalyzed alkoxylation. A broad range enantioenriched alkoxylated phosphinamides were obtained in good yields with excellent enantioselectivities (up 98 % yield >99 ee). An unusual cobalt(III) alcohol complex was prepared fully characterized, which proven be a key intermediate this alkoxylation reaction. Mechanistic studies revealed that oxidation CoIII CoIV facilitated by base whole process proceeded through cobalt(III/IV/II) catalytic cycle.

Язык: Английский

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Electrooxidative Rhodium(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective C−H Annulation of Sulfoximines with Alkynes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(15)

Опубликована: Янв. 30, 2024

Abstract The combination of achiral Cp*Rh(III) with chiral carboxylic acids (CCAs) represents an efficient catalytic system in transition metal‐catalyzed enantioselective C−H activation. However, this hybrid catalysis is limited to redox‐neutral activation reactions and the adopt oxidative remains elusive pose a significant challenge. Herein, we describe development electrochemical Cp*Rh(III)‐catalyzed annulation sulfoximines alkynes enabled by acid (CCA) operationally friendly undivided cell at room temperature. A broad range enantioenriched 1,2‐benzothiazines are obtained high yields excellent enantioselectivities (up 99 % yield 98 : 2 er). practicality method demonstrated scale‐up reaction batch reactor external circulation. crucial intermediate isolated, characterized, transformed, providing rational support for Rh(III)/Rh(I) electrocatalytic cycle.

Язык: Английский

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Recent Advances in Asymmetric Organometallic Electrochemical Synthesis (AOES)

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 19, 2025

ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with transition metal catalysis. On one hand, we have rationalized that compounds can serve as molecular electrocatalysts (mediators) reduce overpotentials and enhance both reactivity selectivity reactions. other conditions for catalysis be substantially improved through electrochemistry, enabling precise modulation metal's oxidation state by controlling potentials regulating electron transfer rate via current adjustments. This synergistic approach addresses key challenges inherent in traditional catalysis, particularly those related use redox-active chemical reagents. Furthermore, redox conveniently tuned modifying their ligands, thereby governing reaction regioselectivity stereoselectivity. As a result, AOES emerged powerful promising tool chiral compounds.In this Account, summarize contextualize efforts AOES. Our primary strategy involves leveraging controllability potential regulate organometallics, facilitating desired An efficient platform was established under mild conditions, significantly reducing reliance on been systematically categorized into three sections based distinct electrolysis modes: combined anodic oxidation, cathodic reduction, paired electrolysis. In each section, highlight innovative discoveries tailored unique characteristics respective modes.In many transformations, metal-catalyzed reactions involving reagents utilizing exhibit similar reactivities. However, also observed notable differences certain cases. These findings include following: (1) Enhanced efficiency synthesis: instance, Rh-catalyzed enantioselective functionalization C–H bonds demonstrates superior efficiency. (2) Expanded scope transformations: previously challenging achieved due tunability potentials. A example is reductive coupling aryl chlorides, expands range accessible transformations. Additionally, mechanistic studies explore techniques intrinsic such controlled experiments, impact electrode materials catalyst performance, cyclic voltammetry studies. investigations provide more intuitive understanding behavior catalysts study mechanisms, guide design new catalytic systems.The advancements offer robust environmentally friendly sustainable selective By integrating developed versatile organic not only enhances but reduces environmental impact. We anticipate Account will stimulate further innovation realm AOES, leading discovery systems development synthetic methodologies.

Язык: Английский

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The applications of electrochemical synthesis in asymmetric catalysis

Chem Catalysis, Год журнала: 2022, Номер 2(11), С. 3019 - 3047

Опубликована: Окт. 27, 2022

Язык: Английский

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Enantioselective Nickel‐Catalyzed Electrochemical Radical Allylation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(38)

Опубликована: Авг. 1, 2022

A simplified and appealing strategy via a chiral catalyst to facilitate the electrochemical process provide asymmetric induction of radical reactions is particularly desirable would have potential applications in electrosynthesis, organic chemistry, drug discovery. Here, we introduced novel electrolytic system that diverts standard ionic reactivity new catalytic functions, enabling mechanistically distinct single-electron transfer-based enantioselective routes exhibit brand-new pattern reactivity-electricity-driven catalysis as privileged platform for allylation. The nickel-catalyzed activation nucleophiles triggered transfer catalyst-bound cation intermediate, which could be applied an alternative development stereocontrolled reactions.

Язык: Английский

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Cobaltaelectro-Catalyzed C–H Annulation with Allenes for Atropochiral and P-Stereogenic Compounds: Late-Stage Diversification and Continuous Flow Scale-Up

ACS Catalysis, Год журнала: 2023, Номер 13(14), С. 9713 - 9723

Опубликована: Июль 11, 2023

The 3d metallaelectro-catalyzed C-H activation has been identified as an increasingly viable strategy to access valuable organic molecules in a resource-economic fashion under exceedingly mild reaction conditions. However, the development of enantioselective is very challenging and its infancy. Here, we disclose merger cobaltaelectro-catalyzed with asymmetric catalysis for highly annulation allenes. A broad range C-N axially chiral P-stereogenic compounds were thereby obtained good yields up 98% high enantioselectivities >99% ee. practicality this approach was demonstrated by diversification complex bioactive drug well decagram scale electrocatalysis continuous flow.

Язык: Английский

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Synthesis of P-stereogenic cyclicphosphinic amidesviaelectrochemically enabled cobalt-catalyzed enantioselective C–H annulation

Green Chemistry, Год журнала: 2023, Номер 25(9), С. 3606 - 3614

Опубликована: Янв. 1, 2023

We describe a cobalta-electro-catalyzed enantioselective C–H annulation of arylphosphinamides with alkynes for P-stereogenic compounds via desymmetrization and kinetic resolution processes.

Язык: Английский

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