3d Transition Metals for C–H Activation

Chemical Reviews, Год журнала: 2018, Номер 119(4), С. 2192 - 2452

Опубликована: Ноя. 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.

Язык: Английский

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Electrocatalytic C–H Activation

ACS Catalysis, Год журнала: 2018, Номер 8(8), С. 7086 - 7103

Опубликована: Июнь 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.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(37), С. 12803 - 12818

Опубликована: Май 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.

Язык: Английский

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Catalytic Transformations of Functionalized Cyclic Organic Carbonates

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(42), С. 13735 - 13747

Опубликована: Июнь 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.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(45), С. 14700 - 14717

Опубликована: Июль 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.

Язык: Английский

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

Chemical Reviews, Год журнала: 2021, Номер 122(3), С. 3180 - 3218

Опубликована: Ноя. 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.

Язык: Английский

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Resource Economy by Metallaelectrocatalysis: Merging Electrochemistry and C H Activation

Trends in Chemistry, Год журнала: 2019, Номер 1(1), С. 63 - 76

Опубликована: Март 8, 2019

Язык: Английский

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

Organic Letters, Год журнала: 2018, Номер 20(17), С. 5523 - 5527

Опубликована: Авг. 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.

Язык: Английский

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Electrochemical Cobalt‐Catalyzed C−H Activation

Chemistry - A European Journal, Год журнала: 2018, Номер 24(61), С. 16209 - 16217

Опубликована: Июнь 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.

Язык: Английский

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Late‐Stage Peptide Diversification through Cobalt‐Catalyzed C−H Activation: Sequential Multicatalysis for Stapled Peptides

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(6), С. 1684 - 1688

Опубликована: Ноя. 30, 2018

Bioorthogonal late-stage diversification of structurally complex peptides has enormous potential for drug discovery and molecular imaging. In recent years, transition-metal-catalyzed C-H activation emerged as an increasingly viable tool peptide modification. Despite major accomplishments, these strategies largely rely on expensive palladium catalysts. We herein report unprecedented cobalt(III)-catalyzed activation, which enables the direct functionalization peptides, sets stage a multicatalytic activation/alkene metathesis/hydrogenation strategy assembly novel cyclic peptides.

Язык: Английский

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