3d Transition Metals for C–H Activation

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2192 - 2452

Published: Nov. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Language: Английский

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Electrocatalytic C–H Activation

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(8), P. 7086 - 7103

Published: June 18, 2018

C–H activation has emerged as a transformative tool in molecular synthesis, but until recently oxidative activations have largely involved the use of stoichiometric amounts expensive and toxic metal oxidants, compromising overall sustainable nature chemistry. In sharp contrast, electrochemical been identified more efficient strategy that exploits storable electricity place byproduct-generating chemical reagents. Thus, transition-metal catalysts were shown to enable versatile reactions manner. While palladium catalysis set stage for C(sp2)–H C(sp3)–H functionalizations by N-containing directing groups, rhodium ruthenium allowed weakly coordinating amides acids. contrast these precious 4d transition metals, recent year witnessed emergence cobalt oxygenations, nitrogenations, C–C-forming [4+2] alkyne annulations. Thereby, silver(I) oxidants was prevented, improving environmentally benign catalysis. Herein, we summarize major advances organometallic otherwise inert bonds electrocatalysis through May 2018.

Language: Английский

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Enantioselective C−H Activation with Earth‐Abundant 3d Transition Metals

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(37), P. 12803 - 12818

Published: May 11, 2019

Molecular syntheses largely rely on time- and labour-intensive prefunctionalization strategies. In contrast, C-H activation represents an increasingly powerful approach that avoids lengthy of prefunctionalized substrates, with great potential for drug discovery, the pharmaceutical industry, material sciences, crop protection, among others. The enantioselective functionalization omnipresent bonds has emerged as a transformative tool step- atom-economical generation chiral molecular complexity. However, this rapidly growing research area remains dominated by noble transition metals, prominently featuring toxic palladium, iridium rhodium catalysts. Indeed, despite significant achievements, use inexpensive sustainable 3d metals in asymmetric activations is still clearly its infancy. Herein, we discuss remarkable recent progress transformations via organometallic base up to April 2019.

Language: Английский

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Catalytic Transformations of Functionalized Cyclic Organic Carbonates

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(42), P. 13735 - 13747

Published: June 6, 2018

Functionalized cyclic organic carbonates and related heterocycles have emerged as highly versatile heterocyclic substrates for ring-opening decarboxylative catalytic transformations allowing the development of new stereo- enantioselective C-N, C-O, C-C, C-S C-B bond formation reactions. Transition-metal-mediated conversions only recently been rejuvenated powerful approaches towards preparation more complex molecules. This minireview will highlight potential structurally with a focus on their synthetic value mechanistic manifolds that are involved upon conversion.

Language: Английский

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Late‐Stage Peptide Diversification by Position‐Selective C−H Activation

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(45), P. 14700 - 14717

Published: July 3, 2018

The late-stage modification of structurally complex peptides bears great potential for drug discovery, crop protection, and the pharmaceutical industry, among others. Whereas traditional approaches largely rely on prefunctionalizations, C-H activation catalysis has in recent years emerged as an increasingly powerful tool post-translational peptide modifications a step-economic manner. Herein, we summarize progress organometallic until June 2018, including position- chemoselective palladium-, ruthenium-, manganese-catalyzed processes.

Language: Английский

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Advances on the Merger of Electrochemistry and Transition Metal Catalysis for Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(3), P. 3180 - 3218

Published: Nov. 19, 2021

Synthetic organic electrosynthesis has grown in the past few decades by achieving many valuable transformations for synthetic chemists. Although electrocatalysis been popular improving selectivity and efficiency a wide variety of energy-related applications, last two decades, there much interest to develop conceptually novel transformations, selective functionalization, sustainable reactions. This review discusses recent advances combination electrochemistry homogeneous transition-metal catalysis synthesis. The enabling mechanistic studies are presented alongside advantages as well future directions address challenges metal-catalyzed electrosynthesis.

Language: Английский

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Resource Economy by Metallaelectrocatalysis: Merging Electrochemistry and C H Activation

Trends in Chemistry, Journal Year: 2019, Volume and Issue: 1(1), P. 63 - 76

Published: March 8, 2019

Language: Английский

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Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4607 - 4647

Published: Jan. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Language: Английский

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Photoredox-Catalyzed Intermolecular Remote C–H and C–C Vinylation via Iminyl Radicals

Organic Letters, Journal Year: 2018, Volume and Issue: 20(17), P. 5523 - 5527

Published: Aug. 23, 2018

A unified strategy for intermolecular remote C(sp3)–H and C–C vinylation of O-acyl oximes with vinyl boronic acids has been achieved. This is enabled by photoreductive generation iminyl radicals from under irradiation visible light. The translocated carbon-centered radicals, which are generated the through 1,5-hydrogen atom transfer or cleavage, can be vinylated acids. opens up a new approach to functionalization via cleavage provides an efficient versatile solution synthesis γ-vinylation ketones nitriles.

Language: Английский

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Electrochemical Cobalt‐Catalyzed C−H Activation

Chemistry - A European Journal, Journal Year: 2018, Volume and Issue: 24(61), P. 16209 - 16217

Published: June 19, 2018

Carbon-heteroatom bonds represent omnipresent structural motifs of the vast majority functionalized materials and bioactive compounds. C-H activation has emerged as arguably most efficient strategy to construct C-Het bonds. Despite major advances, these transformations were largely dominated by precious transition metal catalysts, in combination with stoichiometric, toxic oxidants. Herein, we discuss recent evolution cobalt-catalyzed activations that enable formations electricity sole sustainable oxidant until May 2018.

Language: Английский

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