4.4 Review

Recent Advances in Base Metal (Copper, Cobalt and Nickel)-Catalyzed Directed C-H Amination

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Article Chemistry, Organic

Thiocarbamate-directed Cp*Co(III)-Catalyzed Olefinic C-H Amidation: Facile Access to Enamines with High (Z)-Selectivity

Ya-Ru Liang et al.

Summary: A series of enamines were successfully synthesized through a thiocarbamate-directed Cp*Co(III)-catalyzed C-H oxidative amidation of olefins. The key feature of this protocol is the use of earth-abundant cobalt as catalyst and thiocarbamate as directing group, providing an efficient and simple manner to synthesize enamines in good yields with high (Z)-selectivity under mild conditions.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2021)

Article Chemistry, Organic

C-H Amidation and Amination of Arenes and Heteroarenes with Amide and Amine using Cu-MnO as a Reusable Catalyst under Mild Conditions

Harshvardhan Singh et al.

Summary: This atom-economical and efficient route for the direct amidation and amination of aryl C-H bonds using the synthesized recyclable heterogeneous Cu-MnO catalyst shows excellent results with good to excellent yields under mild conditions; the catalyst can be reused several times without significant loss of reactivity, demonstrating its environmental friendliness and cost-effectiveness.

JOURNAL OF ORGANIC CHEMISTRY (2021)

Article Chemistry, Organic

Copper(II) mediated C-8 amination of 1-naphthylamide derivatives with acyclic and cyclic amines

Tapan Sahoo et al.

Summary: A simple and facile copper(II) mediated protocol for C-8 amination of 1-naphthylamide derivatives using picolinamide as a directing group is reported. Various substituted naphthylamide derivatives react with cyclic and acyclic amines in good yields under mild conditions, with air as the sole oxidant.

TETRAHEDRON LETTERS (2021)

Review Chemistry, Multidisciplinary

Organopalladium Intermediates in Coordination-Directed C(sp3)-H Functionalizations

Anjana Sarala Suseelan et al.

Summary: Transition metal-catalyzed functionalization of dormant C-H bonds is an effective method for diversifying organic molecules, with palladium-based complexes being recognized as front-runners due to their low activation barrier during redox state shuffling. However, achieving exquisite stereoselective C-H activation with Pd-catalysts remains a synthetic challenge, which can be addressed by incorporating interactive directing groups in the catalyst architecture for selective functionalization of desired C-H bonds. The introduction of organopalladium catalysts has shifted the C-H activation chemistry paradigm through rational modulation of the catalytic cycle.

TRENDS IN CHEMISTRY (2021)

Review Chemistry, Multidisciplinary

Site-selective functionalization of remote aliphatic C-H bonds via C-H metallation

Qi Zhang et al.

Summary: The review summarizes recent advancements in achieving selective functionalization of remote C(sp(3))-H bonds in transition metal-catalyzed C-H functionalization reactions, showcasing strategies such as specific substrate selection, switching of the regiodetermining step, utilization of ring strain in metallacycles, multiple non-covalent interactions, and favorable reductive elimination.

CHEMICAL SCIENCE (2021)

Review Chemistry, Multidisciplinary

Ni-Catalyzed Chelation-Assisted Direct Functionalization of Inert C-H Bonds

Yan-Hua Liu et al.

CHINESE JOURNAL OF CHEMISTRY (2020)

Article Chemistry, Multidisciplinary

Synthesis of Chiral β-Lactams by Pd-Catalyzed Enantioselective Amidation of Methylene C(sp3)-H Bonds

Tao Zhou et al.

CHINESE JOURNAL OF CHEMISTRY (2020)

Review Chemistry, Multidisciplinary

Transition Metal-Catalyzed Enantioselective C-H Functionalization via Chiral Transient Directing Group Strategies

Gang Liao et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

Article Chemistry, Organic

Copper(II)-Catalyzed Direct Amination of 1-Naphthylamines at the C8 Site

Conghui Zu et al.

JOURNAL OF ORGANIC CHEMISTRY (2020)

Review Chemistry, Organic

Transition Metal-Catalyzed C-H Activation via Imine-Based Transient Directing Group Strategy

Yongjie Wu et al.

CHINESE JOURNAL OF ORGANIC CHEMISTRY (2020)

Review Chemistry, Multidisciplinary

Radical azidation as a means of constructing C(sp3)-N3 bonds

Liang Ge et al.

GREEN SYNTHESIS AND CATALYSIS (2020)

Article Chemistry, Multidisciplinary

Noncovalent Interaction in Transition Metal-Catalyzed Selective C-H Activation

Liao Gang et al.

ACTA CHIMICA SINICA (2020)

Article Chemistry, Organic

Amide-Directed Cobalt(III)-Catalyzed C-H Amidation of Ferrocenes

Dan-Ying Huang et al.

ORGANIC LETTERS (2019)

Article Chemistry, Multidisciplinary

Synergy of Anodic Oxidation and Cathodic Reduction Leads to Electrochemical C-H Halogenation

Zhilin Zhou et al.

CHINESE JOURNAL OF CHEMISTRY (2019)

Article Chemistry, Inorganic & Nuclear

Chiral 2-Aryl Ferrocene Carboxylic Acids for the Catalytic Asymmetric C(sp3)-H Activation of Thioamides

Daichi Sekine et al.

ORGANOMETALLICS (2019)

Review Chemistry, Multidisciplinary

Mechanistic Development and Recent Applications of the Chan-Lam Amination

Matthew J. West et al.

CHEMICAL REVIEWS (2019)

Review Chemistry, Multidisciplinary

Upgrading Cross-Coupling Reactions for Biaryl Syntheses

Yun-Fei Zhang et al.

ACCOUNTS OF CHEMICAL RESEARCH (2019)

Article Chemistry, Multidisciplinary

Enantioselective C(sp3)-H Amidation of Thioamides Catalyzed by a CobaltIII/Chiral Carboxylic Acid Hybrid System

Seiya Fukagawa et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

Review Chemistry, Multidisciplinary

3d Transition Metals for C-H Activation

Parthasarathy Gandeepan et al.

CHEMICAL REVIEWS (2019)

Review Chemistry, Organic

Enantioselective Synthesis of Atropisomers Featuring Pentatomic Heteroaromatics

Shuo Zhang et al.

CHINESE JOURNAL OF ORGANIC CHEMISTRY (2019)

Review Chemistry, Multidisciplinary

Catalytic alkylation of unactivated C(sp3)-H bonds for C(sp3)-C(sp3) bond formation

Zhen Chen et al.

CHEMICAL SOCIETY REVIEWS (2019)

Article Chemistry, Multidisciplinary

Site- selective C( sp3)- H amination of thioamide with anthranils under Cp* CoIII catalysis

Rui-Hua Liu et al.

CHEMICAL COMMUNICATIONS (2019)

Review Chemistry, Multidisciplinary

Chelation-Assisted Nickel-Catalyzed C-H Functionalizations

Shrikant M. Khake et al.

TRENDS IN CHEMISTRY (2019)

Review Chemistry, Organic

Progress in Copper-Catalyzed Chan-Lam Coupling of N-Compounds

Xiyan Duan et al.

CHINESE JOURNAL OF ORGANIC CHEMISTRY (2019)

Article Chemistry, Multidisciplinary

Electrochemical C-H Amination by Cobalt Catalysis in a Renewable Solvent

Nicolas Sauermann et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

Article Chemistry, Organic

Thiocarbonyl-enabled ferrocene C-H nitrogenation by cobalt(III) catalysis: thermal and mechanochemical

Santhivardhana Reddy Yetra et al.

BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY (2018)

Review Chemistry, Multidisciplinary

Comparison of the Reactivities and Selectivities of Group9 [Cp*M-III] Catalysts in C-H Functionalization Reactions

Juhyeon Park et al.

CHEMISTRY-AN ASIAN JOURNAL (2018)

Article Chemistry, Physical

Cp*Co(III)-catalyzed ortho C-H amidation of 2-pyridinyl ferrocenes with 1,4,2-dioxazol-5-ones

Shao-Bo Wang et al.

JOURNAL OF CATALYSIS (2018)

Article Chemistry, Multidisciplinary

Cobalt(II)-Catalyzed Electrooxidative C-H Amination of Arenes with Alkylamines

Xinlong Gao et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2018)

Review Chemistry, Organic

Transient imines as 'next generation' directing groups for the catalytic functionalisation of C-H bonds in a single operation

Sahra St John-Campbell et al.

ORGANIC & BIOMOLECULAR CHEMISTRY (2018)

Article Chemistry, Multidisciplinary

Copper mediated C-H amination with oximes: en route to primary anilines

Lin-Lin Xu et al.

CHEMICAL SCIENCE (2018)

Review Chemistry, Multidisciplinary

sp3 C-H activation via exo-type directing groups

Yan Xu et al.

CHEMICAL SCIENCE (2018)

Review Chemistry, Multidisciplinary

Transient Directing Groups for Transformative C-H Activation by Synergistic Metal Catalysis

Parthasarathy Gandeepan et al.

Article Chemistry, Applied

Mechanochemical Cobalt-Catalyzed C-H Bond Functionalizations by Ball Milling

Hanchao Cheng et al.

ADVANCED SYNTHESIS & CATALYSIS (2018)

Article Chemistry, Applied

Direct Synthesis of Primary Anilines via Nickel-mediated C(sp(2))-H Aminations

Lin Yu et al.

ADVANCED SYNTHESIS & CATALYSIS (2018)

Review Chemistry, Multidisciplinary

A comprehensive overview of directing groups applied in metal-catalysed C-H functionalisation chemistry

Carlo Sambiagio et al.

CHEMICAL SOCIETY REVIEWS (2018)

Article Chemistry, Multidisciplinary

Copper-Mediated Amination of Aryl C-H Bonds with the Direct Use of Aqueous Ammonia via a Disproportionation Pathway

Hyunwoo Kim et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2018)

Review Chemistry, Multidisciplinary

Palladium-Catalyzed Transformations of Alkyl C-H Bonds

Jian He et al.

CHEMICAL REVIEWS (2017)

Article Chemistry, Organic

Copper-Catalyzed Direct, Regioselective Arylamination of N-Oxides: Studies To Access Conjugated π-Systems

Aniruddha Biswas et al.

JOURNAL OF ORGANIC CHEMISTRY (2017)

Article Chemistry, Organic

Cp☆Co(III)-catalyzed ortho-amidation of azobenzenes with dioxazolones

Gongutri Borah et al.

ORGANIC & BIOMOLECULAR CHEMISTRY (2017)

Article Chemistry, Organic

Co(III)-Catalyzed Enaminone-Directed C-H Amidation for Quinolone Synthesis

Pengfei Shi et al.

ORGANIC LETTERS (2017)

Article Chemistry, Organic

1,2,3-Triazole-assisted C-H amidation by cobalt(III) catalysis

Xinling Yu et al.

ORGANIC CHEMISTRY FRONTIERS (2017)

Article Chemistry, Multidisciplinary

Thioamide-Directed Cobalt(III)-Catalyzed Selective Amidation of C(sp3)-H Bonds

Peng Wen Tan et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2017)

Review Chemistry, Multidisciplinary

Selected Copper-Based Reactions for C-N, C-O, C-S, and C-C Bond Formation

Subhajit Bhunia et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2017)

Article Chemistry, Multidisciplinary

Dibenzothiophene Sulfoximine as an NH3 Surrogate in the Synthesis of Primary Amines by Copper-Catalyzed C-X and C-H Bond Amination

Zhen Li et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2017)

Review Chemistry, Multidisciplinary

Metal-Organic Cooperative Catalysis in C-H and C-C Bond Activation

Dong-Su Kim et al.

CHEMICAL REVIEWS (2017)

Review Chemistry, Multidisciplinary

C-H functionalization by high-valent Cp*Co(III) catalysis

Shan Wang et al.

CHEMICAL COMMUNICATIONS (2017)

Article Chemistry, Applied

Cobalt-Catalyzed Direct Amination of Arenes with Alkylamines via Bidentate-Chelation Assistance

Qiangqiang Yan et al.

ADVANCED SYNTHESIS & CATALYSIS (2016)

Review Chemistry, Applied

Copper-Catalyzed or -Mediated C-H Bond Functionalizations Assisted by Bidentate Directing Groups

Jidan Liu et al.

ADVANCED SYNTHESIS & CATALYSIS (2016)

Article Chemistry, Multidisciplinary

Overcoming the Limitations of C-H Activation with Strongly Coordinating N-Heterocycles by Cobalt Catalysis

Hui Wang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2016)

Article Chemistry, Multidisciplinary

Anthranil: An Aminating Reagent Leading to Bifunctionality for Both C(sp3)-H and C(sp2)-H under Rhodium(III) Catalysis

Songjie Yu et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2016)

Article Chemistry, Multidisciplinary

Cobalt(III)-Catalyzed Intramolecular Cross-Dehydrogenative C-H/X-H Coupling: Efficient Synthesis of Indoles and Benzofurans

Jayanta Ghorai et al.

CHEMISTRY-A EUROPEAN JOURNAL (2016)

Article Chemistry, Multidisciplinary

Cp*CoIII-Catalyzed C(sp3)-H Bond Amidation of 8-Methylquinoline

Nagaraju Barsu et al.

CHEMISTRY-A EUROPEAN JOURNAL (2016)

Article Chemistry, Organic

Copper-Catalyzed Cross-Dehydrogenative Coupling of N-Iminoquinolinium Ylides with Secondary Amines

Zerui Hua et al.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2016)

Article Chemistry, Organic

Copper(II)-Mediated Intermolecular C(sp2)-H Amination of Benzamides with Electron-Rich Anilines

Bijaya Kumar Singh et al.

JOURNAL OF ORGANIC CHEMISTRY (2016)

Article Chemistry, Organic

Copper-Catalyzed Intramolecular Benzylic C-H Amination for the Synthesis of Isoindolinones

Chiaki Yamamoto et al.

JOURNAL OF ORGANIC CHEMISTRY (2016)

Article Chemistry, Multidisciplinary

Direct Hydroxylation and Amination of Arenes via Deprotonative Cupration

Noriyuki Tezuka et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016)

Article Chemistry, Multidisciplinary

A General Method for Aminoquinoline-Directed, Copper-Catalyzed sp2 C-H Bond Amination

James Roane et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016)

Article Chemistry, Organic

Cobalt(II)-Catalyzed C-H Amination of Arenes with Simple Alkylamines

Lin-Bao Zhang et al.

ORGANIC LETTERS (2016)

Article Multidisciplinary Sciences

Functionalization of C(sp3)-H bonds using a transient directing group

Fang-Lin Zhang et al.

SCIENCE (2016)

Review Chemistry, Organic

Recent Progress on Copper-Mediated Directing-Group-Assisted C(sp2)-H Activation

Ming Shang et al.

SYNTHESIS-STUTTGART (2016)

Article Chemistry, Physical

Oxazolinyl-Assisted C-H Amidation by Cobalt(III) Catalysis

Ruhuai Mei et al.

ACS CATALYSIS (2016)

Article Chemistry, Organic

Copper(I) catalyzed C(sp2)-N bond formation: synthesis of pyrrolo[3,2-c]quinolinone derivatives

Zhiguo Zhang et al.

ORGANIC CHEMISTRY FRONTIERS (2016)

Review Chemistry, Organic

Recent advances in copper-mediated chelation-assisted functionalization of unactivated C-H bonds

Wei-Hao Rao et al.

ORGANIC CHEMISTRY FRONTIERS (2016)

Review Chemistry, Multidisciplinary

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

Olafs Daugulis et al.

ACCOUNTS OF CHEMICAL RESEARCH (2015)

Article Chemistry, Applied

Copper(I)-Catalyzed Dehydrogenative Amidation of Arenes Using Air as the Oxidant

Gang Li et al.

ADVANCED SYNTHESIS & CATALYSIS (2015)

Review Chemistry, Multidisciplinary

Transition metal-catalyzed ketone-directed or mediated C-H functionalization

Zhongxing Huang et al.

CHEMICAL SOCIETY REVIEWS (2015)

Article Chemistry, Organic

Synthesis of Indolines by Copper-Mediated Intramolecular Aromatic C-H Amination

Kazutaka Takamatsu et al.

JOURNAL OF ORGANIC CHEMISTRY (2015)

Article Chemistry, Organic

Copper(II)-catalyzed electrophilic amination of quinoline N-oxides with O-benzoyl hydroxylamines

Gang Li et al.

ORGANIC & BIOMOLECULAR CHEMISTRY (2015)

Article Chemistry, Organic

Nickel-Catalyzed Direct Amination of Arenes with Alkylamines

Qiangqiang Yan et al.

ORGANIC LETTERS (2015)

Article Chemistry, Multidisciplinary

Copper-Catalyzed Intramolecular C(sp3)-H and C(sp2)-H Amidation by Oxidative Cyclization

Zhen Wang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2014)

Article Chemistry, Multidisciplinary

Copper-Catalyzed Site-Selective Intramolecular Amidation of Unactivated C( sp3) - H Bonds

Xuesong Wu et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2014)

Article Chemistry, Multidisciplinary

Copper-catalyzed ortho-C-H amination of protected anilines with secondary amines

Angel Manu Martinez et al.

CHEMICAL COMMUNICATIONS (2014)

Article Chemistry, Multidisciplinary

Nickel-Catalyzed Site-Selective Amidation of Unactivated C(sp3)-H Bonds

Xuesong Wu et al.

CHEMISTRY-A EUROPEAN JOURNAL (2014)

Article Chemistry, Organic

A Unified Strategy Towards N-Aryl Heterocycles by a One-Pot Copper-Catalyzed Oxidative C-H Amination of Azoles

Parthasarathi Subramanian et al.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2014)

Article Chemistry, Organic

Cu-Catalyzed Direct Amidation of Aromatic C-H Bonds: An Access to Arylamines

Hui Xu et al.

JOURNAL OF ORGANIC CHEMISTRY (2014)

Article Chemistry, Multidisciplinary

Cu(II)-Mediated C-H Amidation and Amination of Arenes: Exceptional Compatibility with Heterocycles

Ming Shang et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2014)

Article Chemistry, Organic

Synthesis of Carbazoles by Copper-Catalyzed Intramolecular C-H/N-H Coupling

Kazutaka Takamatsu et al.

ORGANIC LETTERS (2014)

Article Chemistry, Organic

Copper-Catalyzed C(sp2)-H Amidation with Azides as Amino Sources

Jiangling Peng et al.

ORGANIC LETTERS (2014)

Article Chemistry, Inorganic & Nuclear

Comparative Investigations of Cp*-Based Group 9 Metal-Catalyzed Direct C-H Amination of Benzamides

Travis M. Figg et al.

ORGANOMETALLICS (2014)

Article Multidisciplinary Sciences

Regioselective ketone α-alkylation with simple olefins via dual activation

Fanyang Mo et al.

SCIENCE (2014)

Article Chemistry, Multidisciplinary

Directed Amination of Non-Acidic Arene CH Bonds by a Copper-Silver Catalytic System

Ly Dieu Tran et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2013)

Article Chemistry, Multidisciplinary

Copper-catalyzed annulation of amidines for quinazoline synthesis

Yunhe Lv et al.

CHEMICAL COMMUNICATIONS (2013)

Article Chemistry, Multidisciplinary

Copper-catalyzed intramolecular direct amination of sp2 C-H bonds for the synthesis of N-aryl acridones

Wang Zhou et al.

CHEMICAL COMMUNICATIONS (2012)

Article Chemistry, Multidisciplinary

Rhodium-Catalyzed Intermolecular Amidation of Arenes with Sulfonyl Azides via Chelation-Assisted C-H Bond Activation

Ji Young Kim et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2012)

Article Chemistry, Organic

Copper-Catalyzed Synthesis of Purine-Fused Polycyclics

Gui-Rong Qu et al.

ORGANIC LETTERS (2012)

Review Chemistry, Multidisciplinary

Cross-Coupling Reactions Of Organoboranes: An Easy Way To Construct C-C Bonds (Nobel Lecture)

Akira Suzuki

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2011)

Article Chemistry, Organic

Copper-Catalyzed Amidation of 2-Phenylpyridine with Oxygen as the Terminal Oxidant

Alex John et al.

JOURNAL OF ORGANIC CHEMISTRY (2011)

Review Chemistry, Multidisciplinary

Palladium-Catalyzed Ligand-Directed C-H Functionalization Reactions

Thomas W. Lyons et al.

CHEMICAL REVIEWS (2010)

Article Chemistry, Multidisciplinary

Pd-Catalyzed Intermolecular ortho-C-H Amidation of Anilides by N-Nosyloxycarbamate

Ka-Ho Ng et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2010)

Review Chemistry, Multidisciplinary

Catalytic C-C, C-N, and C-O Ullmann-Type Coupling Reactions

Florian Monnier et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2009)

Review Chemistry, Multidisciplinary

Palladium(II)-Catalyzed C-H Activation/C-C Cross-Coupling Reactions: Versatility and Practicality

Xiao Chen et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2009)

Review Chemistry, Multidisciplinary

Copper/Amino Acid Catalyzed Cross-Couplings of Aryl and Vinyl Halides with Nucleophiles

Dawei Ma et al.

ACCOUNTS OF CHEMICAL RESEARCH (2008)

Article Chemistry, Multidisciplinary

C-H functionalization/C-N bond formation: Copper-catalyzed synthesis of benzimidazoles from amidines

Gordon Brasche et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2008)

Article Chemistry, Multidisciplinary

Amination of the ortho C-H bonds by the Cu(OAc)2-mediated reaction of 2-phenylpyridines with anilines

Takeshi Uemura et al.

CHEMISTRY LETTERS (2006)

Article Chemistry, Multidisciplinary

Cu(II)-catalyzed functionalizations of aryl C-H bonds using O2 as an oxidant

Xiao Chen et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2006)