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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Mild metal-catalyzed C–H activation: examples and concepts

Chemical Society Reviews, Journal Year: 2016, Volume and Issue: 45(10), P. 2900 - 2936

Published: Jan. 1, 2016

C–H Activation reactions that proceed under mild conditions are more attractive for applications in complex molecule synthesis. Mild transformations reported since 2011 reviewed and the different concepts strategies have enabled their mildness discussed.

Language: Английский

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The medicinal chemist's toolbox for late stage functionalization of drug-like molecules

Chemical Society Reviews, Journal Year: 2015, Volume and Issue: 45(3), P. 546 - 576

Published: Oct. 28, 2015

The advent of modern C-H functionalization chemistries has enabled medicinal chemists to consider a synthetic strategy, late stage (LSF), which utilizes the bonds drug leads as points diversification for generating new analogs. LSF approaches offer promise rapid exploration structure activity relationships (SAR), generation oxidized metabolites, blocking metabolic hot spots and preparation biological probes. This review details toolbox intermolecular with proven applicability drug-like molecules, classified by regioselectivity patterns, gives guidance on how systematically develop strategies using these patterns other considerations. In addition, number examples illustrate have been used impact actual discovery chemical biology efforts.

Language: Английский

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Transition metal-catalyzed C–H bond functionalizations by the use of diverse directing groups

Organic Chemistry Frontiers, Journal Year: 2015, Volume and Issue: 2(9), P. 1107 - 1295

Published: Jan. 1, 2015

In this review, a summary of transition metal-catalyzed C–H activation by utilizing the functionalities as directing groups is presented.

Language: Английский

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Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon–Hydrogen Bonds

Accounts of Chemical Research, Journal Year: 2015, Volume and Issue: 48(4), P. 1053 - 1064

Published: March 10, 2015

ConspectusIn recent years, carbon–hydrogen bond functionalization has evolved from an organometallic curiosity to a tool used in mainstream applications the synthesis of complex natural products and drugs. The use C–H bonds as transformable functional group is advantageous because these are most abundant functionality organic molecules. One-step conversion desired shortens synthetic pathways, saving reagents, solvents, labor. Less chemical waste generated well, showing that this chemistry environmentally beneficial. This Account describes development bidentate, monoanionic auxiliaries for transition-metal-catalyzed reactions. was initially developed overcome limitations with palladium-catalyzed assisted by monodentate directing groups. By electron-rich bidentate groups, unactivated sp3 under palladium catalysis been developed. Furthermore, number base-metal complexes catalyze sp2 bonds. At point, aminoquinoline, picolinic acid, related compounds among versatile moieties chemistry. These groups facilitate catalytic iron, cobalt, nickel, copper, ruthenium, rhodium, complexes. Exceptionally general reactivity observed, enabling, other transformations, direct arylation, alkylation, fluorination, sulfenylation, amination, etherification, carbonylation, alkenylation versatility auxilaries can be attributed following factors. First, they capable stabilizing high oxidation states transition metals, thereby facilitating step. Second, removed, enabling their medicinally relevant substances. While presents significant advance, several methodology apparent. expensive second-row metal catalysts still required efficient functionalization. need install subsequently remove relatively disadvantage.

Language: Английский

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Cobalt-Catalyzed C–H Activation

ACS Catalysis, Journal Year: 2015, Volume and Issue: 6(2), P. 498 - 525

Published: Nov. 24, 2015

Catalytic C–H activation has emerged as a powerful tool for sustainable syntheses. In the recent years, notable success was achieved with development of cobalt-catalyzed functionalizations either in situ generated or single-component cobalt-complexes under mild reaction conditions. Herein, progress field organometallic is reviewed until November 2015.

Language: Английский

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Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(3), P. 1788 - 1887

Published: Jan. 6, 2020

During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for expedient and siteselective construction of C–C bonds. Among various strategies, bidentate groups are now recognized as one most efficient devices selective functionalization certain positions due to fact its metal center permits fine, tunable, reversible coordination. The family permit types assistance be achieved, such N,N-dentate, N,O-dentate, N,S-dentate auxiliaries, which categorized based on coordination site. In this review, we broadly discuss bond reactions formation bonds with aid groups.

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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First-Row Transition-Metal-Catalyzed Carbonylative Transformations of Carbon Electrophiles

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2090 - 2127

Published: May 3, 2018

The main contributions in the field of first-row transition-metal-catalyzed (base-metal-catalyzed) carbonylative transformations have been summarized and discussed. contents divided according to electrophiles applied, followed by different types nucleophiles. Their reaction mechanisms applications emphatically

Language: Английский

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Co(III)-Catalyzed C–H Activation/Formal S_N-Type Reactions: Selective and Efficient Cyanation, Halogenation, and Allylation

Journal of the American Chemical Society, Journal Year: 2014, Volume and Issue: 136(51), P. 17722 - 17725

Published: Dec. 4, 2014

The first cobalt-catalyzed cyanation, halogenation, and allylation via C–H activation have been realized. These formal SN-type reactions generate valuable (hetero)aryl/alkenyl nitriles, iodides, bromides as well allylated indoles using a bench-stable Co(III) catalyst. High regio- mono-selectivity were achieved for these reactions. Additionally, proceeded efficiently with turnover number of 2200 at room temperature, which is unprecedented this Alkenyl substrates amides successfully utilized in Cp*Co(III)-catalyzed the time.

Language: Английский

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