C–H activation

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: June 17, 2021

Language: Английский

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Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(6), P. 5682 - 5841

Published: Oct. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Language: Английский

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Achieving Site-Selectivity for C–H Activation Processes Based on Distance and Geometry: A Carpenter’s Approach

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(24), P. 10571 - 10591

Published: May 21, 2020

The ability to differentiate between highly similar C–H bonds in a given molecule remains fundamental challenge organic chemistry. In particular, the lack of sufficient steric and electronic differences located distal functional groups has prevented development site-selective catalysts with broad scope. An emerging approach circumvent this obstacle is utilize distance target bond coordinating group, along geometry cyclic transition state directed activation, as core molecular recognition parameters multiple bonds. Perspective, we discuss advent recent advances concept. We cover wide range transition-metal-catalyzed, template-directed remote activation reactions alcohols, carboxylic acids, sulfonates, phosphonates, amines. Additionally, review eminent examples which take advantage non-covalent interactions achieve regiocontrol. Continued advancement distance- geometry-based differentiation for regioselective functionalization may lead ultimate realization editing: freedom modify molecules at any site, order.

Language: Английский

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Arene diversification through distal C(sp ² )−H functionalization

Science, Journal Year: 2021, Volume and Issue: 372(6543)

Published: May 13, 2021

Transition metal-catalyzed aryl C-H activation is a powerful synthetic tool as it offers step and atom-economical routes to site-selective functionalization. Compared with proximal ortho-C-H activation, distal (meta- and/or para-) remains more challenging due the inaccessibility of these sites in formation energetically favorable organometallic pretransition states. Directing catalyst toward bonds requires judicious template engineering design, well prudent choice ligands. This review aims summarize recent elegant discoveries exploiting directing group assistance, transient mediators or traceless directors, noncovalent interactions, ligand selection control activation.

Language: Английский

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Transition Metal Catalyzed Enantioselective C(sp²)–H Bond Functionalization

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(23), P. 13748 - 13793

Published: Nov. 12, 2020

Direct catalytic transformation of C–H bonds to new functionalities has provided a powerful strategy synthesize complex molecular scaffolds in straightforward way. Unstinting efforts the synthetic community have helped overcome long-standing major challenge regioselectivity by introducing directing group concept. However, full potential cannot be realized unless activated are stereochemically controlled. The enantioselective bond functionalization could provide an imperative tool for sustainable way synthesizing chiral scaffolds. Despite intrinsic challenges achieving stereocontrol, developed different tools order achieve stereoselective functionalization. In this review, we discuss remarkable recent advances emerging area C(sp2)–H highlight and opportunities, emphasizing techniques so far.

Language: Английский

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Catalytic Enantioselective Functionalizations of C–H Bonds by Chiral Iridium Complexes

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(18), P. 10516 - 10543

Published: Sept. 8, 2020

The development of catalytic enantioselective transformations, enabling the construction complex molecular scaffolds from simple precursors, has been a long-standing challenge in organic synthesis. Recent achievements transition-metal catalyzed functionalizations carbon–hydrogen (C–H) bonds represent promising pathway toward this goal. Over last two decades, iridium catalysis evolved as valuable tool stereocontrolled synthesis chiral molecules via C–H activation. iridium-based systems with various ligand classes, well studies their reaction mechanisms, resulted dynamic progress area. This review aims to present comprehensive picture by complexes emphasis on mechanisms activation step.

Language: Английский

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Metal-catalysed C–H bond activation and borylation

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(12), P. 5042 - 5100

Published: Jan. 1, 2022

Transition metal-catalysed direct borylation of hydrocarbons via C–H bond activation has received a remarkable level attention as popular reaction in the synthesis organoboron compounds owing to their synthetic versatility.

Language: Английский

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Installing the “magic methyl” – C–H methylation in synthesis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(9), P. 5517 - 5563

Published: Jan. 1, 2021

Following notable cases of remarkable potency increases in methylated analogues lead compounds, this review documents the state-of-the-art C–H methylation technology.

Language: Английский

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Recent advances in asymmetric borylation by transition metal catalysis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(23), P. 13129 - 13188

Published: Jan. 1, 2021

We provide a comprehensive overview of transition metal-catalysed asymmetric borylation processes to construct C–B, C–C, and other C–heteroatom bonds with considerable attention devoted the reaction modes mechanisms involved.

Language: Английский

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Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(18), P. 10672 - 10714

Published: Aug. 14, 2020

Enantioselective transition metal catalysis is an area very much at the forefront of contemporary synthetic research. The development processes that enable efficient synthesis enantiopure compounds unquestionable importance to chemists working within many diverse fields central science. Traditional approaches solving this challenge have typically relied on leveraging repulsive steric interactions between chiral ligands and substrates in order raise energy one diastereomeric states over other. By contrast, Review examines alternative tactic which a set attractive noncovalent operating are used control enantioselectivity. Examples where creative approach has been successfully applied render fundamental enantioselective presented discussed. In cases examined, ligand scaffold carefully designed accommodate these interactions, while others, critical was only elucidated subsequent computational mechanistic studies. Through exploration discussion recent reports encompassing wide range reaction classes, we hope inspire continue develop asymmetric transformations based powerful concept.

Language: Английский

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