Cyclopentadienyl complexes of group 9 metals in the total synthesis of natural products

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 471, P. 214744 - 214744

Published: Aug. 12, 2022

Language: Английский

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Rhodium‐Catalyzed Dual C−H Activation for Regioselective Triple Annulation of Enaminones: Access to Polycyclic Naphthopyran Derivatives

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(11), P. 1770 - 1776

Published: March 21, 2023

Abstract Rh‐catalyzed C−H activation of arenes for oxidative annulations with alkynes stands out as a protocol polycyclic scaffolds. This perspective drives us to disclose herein rhodium catalyzed regioselective triple annulation enaminones hydroxyl‐alkynoates via double functionalization naphtho‐pyran Secondary coordination OH in alkynoate dictated the regioselectivity. Initial lactonization occurred chemoselectively on enamine part carbo rhodation followed by reductive elimination. was scalable and has shown high functionality tolerance. KIE studies were done get insight mechanism, some downstream transformations achieved show synthetic potential method.

Language: Английский

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Palladium-Catalyzed Annulations via Sequential C–H Activations of C(sp²)–H/C(sp³)–H or C(sp³)–H/C(sp³)–H Bonds

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6535 - 6546

Published: April 15, 2024

Palladium-catalyzed C–H annulation reactions represent a compelling strategy to construct complex ring systems with high step economy. While there are many approaches annulate structures by activation of single bond, transformations that proceed multiple bonds less explored. This is especially true for examples where one the reacting located at an sp3 center. However, exciting developments in palladium-catalyzed continue expand scope these and provide innovative strategies challenging carbon–carbon bonds. From discoveries, sequential activations have emerged as powerful tool access through C(sp2)–H/C(sp3)–H or C(sp3)–H/C(sp3)–H In this Perspective, we showcase recent use order highlight synthetic potential activation-enabled annulations inspire future disconnections diverse scaffold synthesis.

Language: Английский

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meta‐C−H Arylation of Aniline Derivatives via Palladium/ S,O‐Ligand/Norbornene Cooperative Catalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(5)

Published: Dec. 12, 2023

Aromatic amines are ubiquitous moieties in organic molecules and their direct functionalization is of great interest many research areas due to prevalence pharmaceuticals electronics. While several synthetic tools exist for the ortho- para-functionalization anilines, less reactive meta-position not easy achieve with current methods. To date, meta-C-H arylation aniline derivatives has been restricted either use directing groups & templates, or transformation into anilides quaternary anilinium salts. Herein, we report first general efficient meta-C-H-arylation non-directed via cooperative catalysis a palladium-S,O-ligand-norbornene system. The reaction proceeds under mild conditions wide range aryl iodides, while being operationally simple scalable. Our preliminary mechanistic investigation-including isolation palladium complexes deuterium experiments-reveal useful insights substituent-effects both aniline-substrate norbornene-mediator during activation step.

Language: Английский

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Ru(II)-Catalyzed C–H Functionalization of 2-Arylbenzimidazoles with Iodonium Ylides: A Straightforward Access to Bridgehead Polycyclic N-Heterocycles

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(21), P. 13757 - 13762

Published: Oct. 25, 2022

Herein, we disclose an efficient ruthenium-catalyzed C–H functionalization of 2-arylbenzimidazoles/2-arylimidazoles with iodonium ylides leading to substituted tetracyclic and pentacyclic bridgehead N-heterocycles, wherein ylide acts as a carbene precursor. For the first time, proceeds through Ru–carbenoid intermediate. Further, synthetic utility this protocol was successfully shown for gram-scale synthesis useful transformations.

Language: Английский

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Transition-Metal-Catalyzed C–C Bond Macrocyclization via Intramolecular C–H Bond Activation

Catalysts, Journal Year: 2023, Volume and Issue: 13(2), P. 438 - 438

Published: Feb. 17, 2023

Macrocycles are commonly synthesized via late-stage macrolactamization and macrolactonization. Strategies involving C–C bond macrocyclization have been reported, examples include the transition-metal-catalyzed ring-closing metathesis coupling reactions. In this mini-review, we summarize recent progress in direct synthesis of polyketide polypeptide macrocycles using a C–H activation strategy. first part, rhodium-catalyzed alkene–alkene for is described. The second part summarizes macrocycles. indolyl aryl C(sp2)–H bonds followed by with various partners such as halides, arylates, alkynyl bromide then documented. Moreover, reactions alkyl C(sp3)–H also included. We hope that mini-review will inspire more researchers to explore new broadly applicable strategies intramolecular activation.

Language: Английский

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Selective Functionalization of 2-Phenyl-4H-Benzo[d][1,3]oxazin-4-ones via C-H Activation

Tetrahedron, Journal Year: 2025, Volume and Issue: 173, P. 134466 - 134466

Published: Jan. 10, 2025

Language: Английский

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An Umpolung Approach for C2‐Selective C−H Amination of Azines by Palladium Catalysis

ChemistryEurope, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Abstract The site‐selective C−H amination of azines is a critical challenge due to the broad applications amino in biologically important compounds. In this work, we report conceptually novel approach electrophilic C2‐selective using O ‐benzoylhydroxylamines, catalyzed by benzyl–palladium complex. A key feature transformation formation distal C−N bond via benzyl–Pd intermediate, facilitated malonate substituent on azine as remote directing group. This strategy effectively overrides inherent polarity mismatch typically observed C2‐C−H aminations. reaction exhibits high site‐selectivity and demonstrates towards amine‐sensitive functional group, highlighting its synthetic utility.

Language: Английский

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Insights into the mechanism of 3d transition-metal-catalyzed directed C(sp³)–H bond functionalization reactions

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review provides an overview of the research advaces in Ni-, Cu-, Fe- and Co-catalyzed directed C(sp 3 )–H bond functionalization reactions; including design principles, mechanistic discussions, along with potential applications limitations.

Language: Английский

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Electron-Deficient CpRh(III)-Catalyzed C–H Functionalization of N-2-Pyridylanilines: Branch-Selective Alkenylation with Alkenes and Annulation with Alkynes

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

We report the electron-deficient CpRh(III) [CpERh(III)] complex-catalyzed branch selective alkenylation with aliphatic alkenes and annulation internal alkynes using N-2-pyridylanilines. In these reactions, CpERh(III) catalyst is more active than electron-rich Cp*Rh(III) catalyst, used commonly in C–H activation, reactions proceed a catalytic amount of Cu(II) oxidant under air at lower temperatures conventional methods. From mechanistic considerations, steric repulsion between ligand directing group may be responsible for alkenylation.

Language: Английский

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