Atroposelective catalysis

Nature Reviews Chemistry, Год журнала: 2024, Номер 8(7), С. 497 - 517

Опубликована: Июнь 18, 2024

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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Enantioselective organocatalytic synthesis of axially chiral aldehyde-containing styrenes via SNAr reaction-guided dynamic kinetic resolution

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Авг. 19, 2023

The precise and efficient construction of axially chiral scaffolds, particularly toward the aryl-alkene atropoisomers with impeccably full enantiocontrol highly structural diversity, remains greatly challenging. Herein, we disclose an organocatalytic asymmetric nucleophilic aromatic substitution (SNAr) reaction aldehyde-substituted styrenes involving a dynamic kinetic resolution process via hemiacetal intermediate, offering novel facile way to significant axial styrene scaffolds. Upon treatment aldehyde-containing bearing (o-hydroxyl)aryl unit commonly available fluoroarenes in presence peptide-phosphonium salts, SNAr exquisite bridged biaryl lactol intermediate undergoes smoothly furnish series decorated various functionalities bioactive fragments high stereoselectivities (up >99% ee) complete E/Z selectivities. These resulting motifs are important building blocks for preparation diverse functionalized styrenes, which have great potential as privileged ligands/catalysts synthesis.

Язык: Английский

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Design and Application of New Pyridine-Derived Chiral Ligands in Asymmetric Catalysis

Accounts of Chemical Research, Год журнала: 2024, Номер 57(6), С. 957 - 970

Опубликована: Март 6, 2024

ConspectusThe innovation of chiral ligands has been crucial for the asymmetric synthesis functional molecules, as demonstrated by several types widely applied "privileged" ligands. In this context, pyridine-derived ligands, far some oldest and most utilized in catalysis, have attracted considerable research interest past half-century. However, development broadly applicable pyridine units (CPUs) plagued intertwining challenges, thus delaying advancements many reactions.This Account aims to summarize recent progress new CPU-containing focusing on a rationally designed, modular, tunable CPU developed our laboratory. A significant problem thwarting conventional designs is paradox between broad reactivity stereoselectivity; that is, while enhanced stereoselectivity may be achieved introducing elements close N atom, concomitant increase local steric hindrance often limits catalytic activity scope. Our newly features rigid [6-5-3] fused-ring framework spirocyclic ketal side wall. The well-defined three-dimensional structure minimizes (inner layer) tunes peripheral environment (outer remote substituents, securing stereoselectivity. Different chelating were readily assembled using structural module, with applications mechanistically diverse transition-metal-catalyzed reactions. Thus, series 2,2′-bipyridine successfully employed general, efficient, highly enantioselective nickel-catalyzed intermolecular reductive addition, Ullmann coupling ortho-chlorinated aryl aldehydes, carboxylation benzylic (pseudo)halides CO2. Notably, these exhibited superior reactions compared common N-based iridium-catalyzed C–H borylation was N,B-bidentate ligand. Furthermore, challenging, additive-free, broad-scope transfer hydrogenative direct amination half-sandwich iridium catalyst supported N,C-bidentate excellent performance high stereoselectivity, which, when combined experimental computational mechanistic investigations, "double-layer control" design concept.Considering described herein should inspire creation novel catalysts drive

Язык: Английский

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Nickel‐Catalyzed Enantioconvergent Carboxylation Enabled by a Chiral 2,2′‐Bipyridine Ligand

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(51)

Опубликована: Окт. 27, 2022

In contrast to previous approaches chiral α-aryl carboxylic acids that based on reactions using hazardous gases, pressurized setup and mostly noble metal catalysts, in this work, a nickel-catalyzed general, efficient highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides under mild conditions atmospheric CO2 has been developed. A unique 2,2'-bipyridine ligand named Me-SBpy featuring compact polycyclic skeleton enabled both high reactivity stereoselectivity. The utility method demonstrated by synthesis various (30 examples, up 95 % yield 99 : 1 er), including profen family anti-inflammatory drugs transformations the as key intermediates. Based mechanistic experimental results, plausible catalytic cycle involving Ni-complex/radical equilibrium Lewis acid-assisted activation proposed.

Язык: Английский

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A fruitful century for the scalable synthesis and reactions of biphenyl derivatives: applications and biological aspects

RSC Advances, Год журнала: 2023, Номер 13(27), С. 18262 - 18305

Опубликована: Янв. 1, 2023

This review provides recent developments in the current status and latest synthetic methodologies of biphenyl derivatives.

Язык: Английский

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Enantioconvergent synthesis of axially chiral amides enabled by Pd-catalyzed dynamic kinetic asymmetric aminocarbonylation

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

Опубликована: Авг. 23, 2024

Atropisomeric biaryls bearing carbonyl groups have attracted increasing attention due to their prevalence in diverse bioactive molecules and crucial role as efficient organo-catalysts or ligands asymmetric transformations. However, preparation often involves tedious multiple steps, the direct synthesis via carbonylation has scarcely been investigated. Herein, we report an palladium-catalyzed enantioconvergent aminocarbonylation of racemic heterobiaryl triflates with amines dynamic kinetic transformation (DyKAT). This protocol features a broad substrate scope excellent compatibility for rapid construction axially chiral amides good high yields enantioselectivities. Detailed mechanistic investigations discover that base can impede intramolecular hydrogen bond-assisted axis rotation products, thus allowing success achieve enantioselectivity. Moreover, achieved be directly utilized N,N,N-pincer copper-catalyzed enantioselective formation C(sp3)-N C(sp3)-P bonds. Axially containing not only exist various drug candidates but also serve authors transformation.

Язык: Английский

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Diastereo- and enantioselective synthesis of biaryl aldehydes bearing both axial and central chirality

Chemical Communications, Год журнала: 2023, Номер 59(30), С. 4487 - 4490

Опубликована: Янв. 1, 2023

An unprecedented method for the synthesis of biaryl aldehydes bearing both axial and central chirality is presented.

Язык: Английский

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Kinetics and Mechanism of PPh₃/Ni-Catalyzed, Zn-Mediated, Aryl Chloride Homocoupling: Antagonistic Effects of ZnCl₂/Cl^–

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(43), С. 29913 - 29927

Опубликована: Окт. 18, 2024

The Ni/PPh

Язык: Английский

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Access to Axially Chiral Biaryl Benzylamines via Ancestral Enzyme-Enabled Reductive Amination Desymmetrization

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1522 - 1531

Опубликована: Янв. 11, 2025

Axially chiral biaryl benzylamines are present in numerous natural products, pharmaceuticals, ligands, and catalysts. However, the direct catalytic synthesis of these functional molecules using a robust strategy remains formidable challenge. Reductive amination desymmetrization dialdehydes offers powerful approach for construction axially but suffers from extensive undesirable side reactions. Herein, we engineered ancestral imine reductases to enable reductive dialdehydes, allowing wide range with up 99% conversion enantiomeric excess (ee). The ratio product byproducts was 97:3 over 90:10 most cases. This work presents an alternative accessing will stimulate development associated bioactive catalysts/ligands.

Язык: Английский

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