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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Organic synthesis provides opportunities to transform drug discovery

Nature Chemistry, Journal Year: 2018, Volume and Issue: 10(4), P. 383 - 394

Published: March 22, 2018

Language: Английский

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Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1485 - 1542

Published: Nov. 18, 2021

The merger of photoredox catalysis with transition metal catalysis, termed metallaphotoredox has become a mainstay in synthetic methodology over the past decade. Metallaphotoredox combined unparalleled capacity for bond formation broad utility photoinduced electron- and energy-transfer processes. Photocatalytic substrate activation allowed engagement simple starting materials metal-mediated bond-forming Moreover, electron or energy transfer directly key organometallic intermediates provided novel modes entirely complementary to traditional catalytic platforms. This Review details contextualizes advancements molecule construction brought forth by metallaphotocatalysis.

Language: Английский

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New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(5), P. 2613 - 2692

Published: Feb. 17, 2020

Transition-metal catalyzed reactions that are able to construct complex aliphatic amines from simple, readily available feedstocks have become a cornerstone of modern synthetic organic chemistry. In light the ever-increasing importance across range chemical sciences, this review aims provide concise overview transition-metal approaches alkylamine synthesis and their functionalization. Selected examples amine bond forming include: (a) hydroamination hydroaminoalkylation, (b) C(sp3)–H functionalization, (c) visible-light-mediated photoredox catalysis.

Language: Английский

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Photocatalytic decarboxylative alkylations mediated by triphenylphosphine and sodium iodide

Science, Journal Year: 2019, Volume and Issue: 363(6434), P. 1429 - 1434

Published: March 28, 2019

Most photoredox catalysts in current use are precious metal complexes or synthetically elaborate organic dyes, the cost of which can impede their application for large-scale industrial processes. We found that a combination triphenylphosphine and sodium iodide under 456-nanometer irradiation by blue light-emitting diodes catalyze alkylation silyl enol ethers decarboxylative coupling with redox-active esters absence transition metals. Deaminative using Katritzky's N-alkylpyridinium salts trifluoromethylation Togni's reagent also demonstrated. Moreover, phosphine/iodide-based system catalyzes Minisci-type N-heterocycles operate tandem chiral phosphoric acids to achieve high enantioselectivity this reaction.

Language: Английский

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Photoredox-Catalyzed C–H Functionalization Reactions

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1925 - 2016

Published: Sept. 29, 2021

The fields of C–H functionalization and photoredox catalysis have garnered enormous interest utility in the past several decades. Many different scientific disciplines relied on strategies including natural product synthesis, drug discovery, radiolabeling, bioconjugation, materials, fine chemical synthesis. In this Review, we highlight use reactions. We separate review into inorganic/organometallic catalysts organic-based catalytic systems. Further subdivision by reaction class─either sp2 or sp3 functionalization─lends perspective tactical for these methods synthetic applications.

Language: Английский

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The Persistent Radical Effect in Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(1), P. 74 - 108

Published: May 22, 2019

Abstract Radical–radical couplings are mostly nearly diffusion‐controlled processes. Therefore, the selective cross‐coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if have lifetimes they generated at equal rates, will become dominant process. This high cross‐selectivity based on kinetic phenomenon called persistent radical effect (PRE). In this Review, an explanation PRE supported by simulations simple model systems provided. Radical stabilities discussed within context their lifetimes, various examples PRE‐mediated radical–radical in synthesis summarized. It shown that restricted to coupling with transient radical. If one partner longer‐lived than other radical, operates achieved. important point expands scope chemistry. The Review divided into parts, namely 1) or organic 2) “radical–metal crossover reactions”; here, metal‐centered species more generally transition‐metal complexes able react discussed—a field has flourished recently.

Language: Английский

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Selective functionalization of methane, ethane, and higher alkanes by cerium photocatalysis

Science, Journal Year: 2018, Volume and Issue: 361(6403), P. 668 - 672

Published: July 26, 2018

With the recent soaring production of natural gas, use methane and other light hydrocarbon feedstocks as starting materials in synthetic transformations is becoming increasingly economically attractive, although it remains chemically challenging. We report development photocatalytic C-H amination, alkylation, arylation methane, ethane, higher alkanes under visible irradiation at ambient temperature. High catalytic efficiency (turnover numbers up to 2900 for 9700 ethane) selectivity were achieved using abundant, inexpensive cerium salts photocatalysts. Ligand-to-metal charge transfer excitation generated alkoxy radicals from simple alcohols that turn acted hydrogen atom catalysts. The mixed-phase gas/liquid reaction was adapted continuous flow, enabling efficient gaseous scalable transformations.

Language: Английский

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Late-stage C–H functionalization offers new opportunities in drug discovery

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(8), P. 522 - 545

Published: July 13, 2021

Language: Английский

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Alkyl Carbon–Carbon Bond Formation by Nickel/Photoredox Cross‐Coupling

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(19), P. 6152 - 6163

Published: Oct. 6, 2018

The union of photoredox and nickel catalysis has resulted in a renaissance radical chemistry as well the use nickel-catalyzed transformations, specifically for carbon-carbon bond formation. Collectively, these advances address longstanding challenge late-stage cross-coupling functionalized alkyl fragments. Empowered by notion that photocatalytically generated radicals readily undergo capture Ni complexes, wholly new feedstocks have been realized. Herein, we highlight recent developments several types cross-couplings are accessible exclusively through this approach.

Language: Английский

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