Transition-metal catalyzed C–H activation as a means of synthesizing complex natural products

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(21), P. 7461 - 7503

Published: Jan. 1, 2023

Over the past few decades, advent of C–H activation has led to a rethink among chemists about synthetic strategies employed for multi-step transformations.

Language: Английский

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Ruthenium‐Catalyzed Stereo‐ and Site‐Selective ortho‐ and meta‐C−H Glycosylation and Mechanistic Studies

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(32)

Published: June 8, 2022

Abstract C‐aryl glycosides are popular basic skeletons in biochemistry and pharmaceutical chemistry. Herein, ruthenium‐catalyzed highly stereo‐ site‐selective ortho ‐ meta ‐C Ar −H glycosylation is described. A series of pyranosides furanosides were synthesized by this method. The strategy showed good substrate scope, various N ‐heterocyclic directing groups compatible with the reaction system. mechanistic study suggested that key pathway might involve oxidative addition/reduction elimination, whereas aryl ‐C−H was mediated σ ‐activation. Density functional theory calculations also high stereoselectivity due to steric hindrance.

Language: Английский

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Late-stage meta-C–H alkylation of pharmaceuticals to modulate biological properties and expedite molecular optimisation in a single step

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: April 18, 2024

Catalysed C-H activation has emerged as a transformative platform for molecular synthesis and provides new opportunities in drug discovery by late-stage functionalisation (LSF) of complex molecules. Notably, small aliphatic motifs have gained significant interest medicinal chemistry their beneficial properties applications sp

Language: Английский

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Pd-catalyzed regioselective activation of C(sp²)–H and C(sp³)–H bonds

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Differentiating between two highly similar C-H bonds in a given molecule remains fundamental challenge synthetic organic chemistry. Directing group assisted strategies for the functionalisation of proximal has been known last few decades. However, distal bond is strenuous and requires distinctly specialised techniques. In this review, we summarise advancement Pd-catalysed C(sp

Language: Английский

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High content Fe(III) electrocatalyst for the oxygen reduction and evolution reactions. Spectroscopic, electrochemical, and theoretical insights

International Journal of Hydrogen Energy, Journal Year: 2025, Volume and Issue: 101, P. 605 - 616

Published: Jan. 5, 2025

Language: Английский

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Photo‐Induced Ruthenium‐Catalyzed Double Remote C(sp²)−H / C(sp³)−H Functionalizations by Radical Relay

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(32)

Published: May 9, 2022

Distal C(sp2 )-H and C(sp3 functionalizations have recently emerged as step-economical tools for molecular synthesis. However, while the )-C(sp3 ) construction is of fundamental importance, its formation through double remote )-H/C(sp3 activation has proven elusive. By merging ruthenium-catalyzed meta-C(sp2 functionalization with an aliphatic hydrogen atom transfer (HAT) process, we, herein, describe catalyzed twofold via photo-induced ruthenium-mediated radical relay. Thus, arene bonds alkane were activated by a single catalyst in operation. This process was accomplished at room temperature visible light-notably without exogenous photocatalysts. Experimental computational theory studies uncovered manifold comprising ortho-C-H activation, single-electron-transfer (SET), 1,n-HAT (n=5-7) σ-activation means ruthenium(II) catalyst.

Language: Английский

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Quinoline-based metal complexes: Synthesis and applications

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 499, P. 215453 - 215453

Published: Oct. 24, 2023

Language: Английский

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Visible-Light-Mediated Bimetal-Catalyzed meta-Alkylation of Arenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 427 - 432

Published: Jan. 8, 2024

A mild approach to the visible-light-mediated bimetal-catalyzed meta-alkylation of arenes has been accomplished. The regioselective is realized by a bimetallic ruthenium–palladium system. Ruthenium acts as catalyst for directing effect and photosensitizer, while cocatalyst palladium behaves generation fluoroalkyl radicals. This reaction not only suitable two-component meta-fluoroalkylation but can also be extended three-component reactions achieve bifunctionalization olefins.

Language: Английский

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Dative Bonding Activation Enables Precise Functionalization of the Remote B–H Bond of nido-Carborane Clusters

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

The innovation of synthetic strategies for selective B-H functionalization is a pivotal objective in the realm boron cluster chemistry. However, precise, efficient, and rapid bond carboranes that distant from existing functional groups remains intractable owing to limited approaches site-selective control established methods. Herein, we report dative bonding activation strategy nonclassical remote site

Language: Английский

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Nickel-Catalyzed Functionalization Reactions Involving C–H Bond Activation via an Amidate-Promoted Strategy and Its Extension to the Activation of C–F, C–O, C–S, and C–CN Bonds

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(21), P. 3053 - 3064

Published: Oct. 11, 2023

ConspectusThe development of functionalization reactions involving the activation C-H bonds has evolved extensively due to atom and step economy associated with such reactions. Among these reactions, chelation assistance been shown provide a powerful solution serious issues reactivity regioselectivity faced in bonds. The vast majority reported thus far involved use precious metals. Kleiman Dubeck cyclonickelation azobenzene NiCp2 which an azo group directs Ni center activate ortho bond close proximity. Although this stoichiometric reaction was discovered earlier than that for other transition-metal complexes, its as catalytic delayed. No general systems were available Ni-catalyzed long time. This Account details our group's Ni(0)- Ni(II)-catalyzed chelation-assisted It also highlights how new strategy can be extended unreactive bonds.In early 2010s, we found Ni(0)-catalyzed aromatic amides contain 2-pyridinylmethylamine moiety directing alkynes results C-H/N-H oxidative annulation give isoquinolinones. In addition, combination Ni(II) catalyst 8-aminoquinoline superior developing wide variety various electrophiles. proposed include formation unstable Ni(IV) and/or Ni(III) species; generation high-valence species rare at time, but since then, many papers dealing DFT organometallic studies have appeared literature attempts understand mechanism. Based on in-depth considerations mechanism respect why N,N-bidentate is required, realized N-Ni by addition N-H Ni(0) or ligand exchange between key step. We concluded precoordination N(sp2) positions proximity permits bond. working hypothesis, carried out using KOtBu base do not specific desired isoquinolinone, amidate anion acts actual group. Remarkably, applicable C-F, C-O, C-S, C-CN.

Language: Английский

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