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C–H Activation

The possibility of direct introduction of a new functionality (or a new C–C bond) via direct C–H bond transformation is a highly attractive strategy in covalent synthesis. The range of substrates is virtually unlimited, including hydrocarbons, complex organic compounds of small molecular weight, and synthetic and biological polymers. Below is a list of recent articles on this topic. For a review, see

  1. Xiao Chen, Keary M. Engle, Dong-Hui Wang, Jin-Quan Yu*
    Palladium(II)-Catalyzed C–H Activation/C–C Cross-Coupling Reactions: Versatility and Practicality
    Angew. Chem. 2009, 121, 5196–5217; Angew. Chem. Int. Ed. 2009, 48, 5094–5115

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Recent Articles

An Approach to Five-Membered Lactams from Aliphatic Amides and Terminal Acetylenes by Nickel Catalysis

An Approach to Five-Membered Lactams from Aliphatic Amides and Terminal Acetylenes by Nickel Catalysis

[Full Paper]
Cong Lin, Jitan Zhang, Zhengkai Chen, Yue Liu, Zhanxiang Liu, Yuhong Zhang
Adv. Synth. Catal., May 24, 2016, DOI: 10.1002/adsc.201600080. Read article.

Rhodium-Catalyzed/Copper-Mediated Selective C2 Alkynylation of Indoles and C1 Alkynylation of Carbazoles with γ-Substituted tert-Propargyl Alcohols

Rhodium‐Catalyzed/Copper‐Mediated Selective C2 Alkynylation of Indoles and C1 Alkynylation of Carbazoles with γ‐Substituted tert‐Propargyl Alcohols

Pathway to indol derivatives: A rhodium-catalyzed/copper-mediated C2-selective C−H alkynylation of indoles is introduced that uses γ-substituted tert-propargyl alcohols as the alkynylating reagent and a removable 6-methylpyridin-2-yl as the directing group. This strategy can be extended to the C−H alkynylation of carbazoles at the C1 position.

[Full Paper]
Ting Li, Zhen Wang, Wen-Bing Qin, Ting-Bin Wen
ChemCatChem, May 19, 2016, DOI: 10.1002/cctc.201600218. Read article

Heterogeneous Catalytic Hydroarylation of Olefins at a Nanoscopic Aluminum Chlorofluoride

Heterogeneous Catalytic Hydroarylation of Olefins at a Nanoscopic Aluminum Chlorofluoride

ACF – A catalysis first: Aluminum chlorofluoride (ACF) catalyzes the hydroarylation of olefins under remarkably mild conditions, including conversions of fluorinated arenes. The extraordinarily strong Lewis acid character of the amorphous solid facilitates the formation of carbocation-like species from alkenes and fluoroalkenes and subsequent C−C coupling processes.

[Full Paper]
Beatriz Calvo, Jan Wuttke, Thomas Braun, Erhard Kemnitz
ChemCatChem, May 18, 2016, DOI: 10.1002/cctc.201600257. Read article

Synthesis of β-Hydroxysulfides from Thiophenols and Disulfides with tert-Butyl Hydroperoxide as the Oxidant and Reactant

Synthesis of β‐Hydroxysulfides from Thiophenols and Disulfides with tert‐Butyl Hydroperoxide as the Oxidant and Reactant

Quick to react: A procedure for the oxidative synthesis of β-hydroxysulfides is reported, in which thiophenols or diaryl disulfides are reacted with tert-butyl hydroperoxide (TBHP). In the presence of zinc iodide or potassium iodide, with TBHP as the oxidant and pre-reactant, thiophenols and diaryl disulfides react with the methyl group of tBuOH smoothly and selectivity to give the corresponding 2-methyl-1-(arylthio)propan-2-ols as the terminal products in moderate to good yields.

[Communication]
Jian-Bo Feng, Xiao-Feng Wu
ChemistryOpen, May 17, 2016, DOI: 10.1002/open.201600023. Read article

Rh(III)-Catalyzed Hydroarylation of Internal Alkynes Through C-H Bond Activation

Rh(III)-catalyzed hydroarylation of internal alkynes via C-H bond activation was described herein using N,N-dimethylaminocarbonyl as directing group without the need of an external oxidant. This protocol exhibits an exceptional functionality-compatibility due to its extremely mild reaction condition, which provides a facile and highly efficient synthetic method for olefin moieties introduction.

[Communication]
Teck Peng Loh, Chao Feng, Cheng-Qiang Wang
Asian J. Org. Chem., May 11, 2016, DOI: 10.1002/ajoc.201600144. Read article

Manganese-Catalyzed ortho-C-H Alkenylation of Aromatic N-H Imidates with Alkynes: Versatile Access to Mono-Alkenylated Aromatic Nitriles

Manganese-Catalyzed ortho-C-H Alkenylation of Aromatic N-H Imidates with Alkynes: Versatile Access to Mono-Alkenylated Aromatic Nitriles

[Communication]
Xiaoxu Yang, Xiqing Jin, Congyang Wang
Adv. Synth. Catal., May 9, 2016, DOI: 10.1002/adsc.201600128. Read article.

Ligand-Assisted Palladium(II)/(IV) Oxidation for sp3 C-H Fluorination

Ligand-Assisted Palladium(II)/(IV) Oxidation for sp3 C-H Fluorination

[Full Paper]
Huan Sun, Yi Zhang, Ping Chen, Yun-Dong Wu, Xinhao Zhang, Yong Huang
Adv. Synth. Catal., April 13, 2016, DOI: 10.1002/adsc.201600015. Read article.

Organo- and Organometallic-Catalytic Intramolecular [1,5]-Hydride Transfer/Cyclization Process through C(sp3)–H Bond Activation

Organo‐ and Organometallic‐Catalytic Intramolecular [1,5]‐Hydride Transfer/Cyclization Process through C(sp3)–H Bond Activation

Organocatalysts have been successfully used for C(sp3)–H functionalization reactions including redox-neutral processes. In this account, we present a tentative summary of organo- and organometallic-catalytic internal redox cascade reactions with respect to the mechanism, the reactivity of hydrogen donors and acceptors, and the migration modes of hydrogen.

[Personal Account]
Su Jin Kwon, Dae Young Kim
The Chemical Record, April 07, 2016, DOI: 10.1002/tcr.201600003. Read article

Transition-Metal-Catalyzed Direct Addition of Aryl C–H Bonds to Unsaturated Electrophiles

Transition‐Metal‐Catalyzed Direct Addition of Aryl C–H Bonds to Unsaturated Electrophiles

The direct addition of C–H bonds to unsaturated bonds represents a greener alternative to the classical nucleophilic addition using organometallic reagents and has profound synthetic potential because it offers a more straightforward and economical route to many useful compounds without the pre-generation of organometallic reagents from stoichiometric halides. In this account, we demonstrate our contributions to the direct insertion of aromatic C–H bonds into polar C=C, C=N, and C=O bonds via directing-group-assisted and transition-metal-catalyzed tandem reactions.

[Personal Account]
Xian-Ying Shi, Wen-Jing Han, Chao-Jun Li
The Chemical Record, April 05, 2016, DOI: 10.1002/tcr.201500250. Read article

C–H Functionalization on Carbohydrates

C–H Functionalization on Carbohydrates

All positions in carbohydrates have been functionalized through C–H bond cleavage, hence paving the way for easy access to complex modified sugars or natural products. This review presents the methods available for C–H functionalization in carbohydrate chemistry and gives an overview position-by-position.

[Microreview]
Tobias Gylling Frihed, Mikael Bols, Christian Marcus Pedersen
Eur. J. Org. Chem., March 21, 2016, DOI: 10.1002/ejoc.201600121. Read article.

Transition Metal Mediated C–H Activation and Functionalization: The Role of Poly(pyrazolyl)borate and Poly(pyrazolyl)alkane Ligands

Transition Metal Mediated C–H Activation and Functionalization: The Role of Poly(pyrazolyl)borate and Poly(pyrazolyl)alkane Ligands

This microreview presents work surrounding the development and study of Tp-supported platinum group metal complexes for stoichiometric and catalytic C–H bond activation. From κ2- and κ3-coordination modes to increased sterics to electronic parameters, Tp and related ligands have played an important role in the observed reactivity of Ru, Rh and Pt-mediated C–H bond activation reactions.

[Microreview]
Bradley A. McKeown, John P. Lee, Jiajun Mei, Thomas R. Cundari, T. Brent Gunnoe
Eur. J. Inorg. Chem., February 12, 2016, DOI: 10.1002/ejic.201501470. Read article.

Allylic C–H Activation of Olefins by a TpMe2IrIII Compound

Allylic C–H Activation of Olefins by a TpMe2IrIII Compound

The IrIII complex [TpMe2Ir(C6H5)2(N2)] [TpMe2 = hydridotris(3,5-dimethylpyrazolyl)borate] reacts with different olefins to yield organometallic compounds that derive from allylic C–H activations in processes that also generate organic coupling products that involve the vinylic positions of the olefin.

[Full Paper]
Crispín Cristóbal, Laura L. Santos, Rubén Gutiérrez-González, Eleuterio Alvarez, Margarita Paneque, Manuel L. Poveda
Eur. J. Inorg. Chem., January 19, 2016, DOI: 10.1002/ejic.201501253. Read article.

Homo- and Heterodinuclear Ir and Rh Imine-functionalized Protic NHC Complexes: Synthetic, Structural Studies, and Tautomerization/Metallotropism Insights

Homo- and Heterodinuclear Ir and Rh Imine-functionalized Protic NHC Complexes: Synthetic, Structural Studies, and Tautomerization/Metallotropism Insights

Two in one: The Ir–imine-functionalized protic N-heterocyclic carbene (pNHC) complex was obtained through a chelate-assisted C2-H bond activation in the cationic Nimidazole-Ir complex. New homo- and heterodinuclear complexes could be prepared by in situ deprotonation of either the neutral Nimidazole-Ir complex or the Ir pNHC complex followed by addition of metal precursors (see scheme).

[Full Paper]
Fan He, Marcel Wesolek, Andreas A. Danopoulos, Pierre Braunstein
Chem. Eur. J., January 15, 2016, DOI: 10.1002/chem.201504030. Read article.

Enantioselective Access to Spirocyclic Sultams by Chiral Cpx–Rhodium(III)-Catalyzed Annulations

Enantioselective Access to Spirocyclic Sultams by Chiral Cpx–Rhodium(III)-Catalyzed Annulations

Ligands of tomorrow: Chiral spirocyclic sultams are rapidly assembled in a [3+2] annulation from N-sulfonyl ketimines and alkynes. The transformation is catalyzed by rhodium complexes equipped with the atropchiral biaryl Cpx ligand, and provides the sultams in excellent yields and high enantioselectivities.

[Communication]
Manh V. Pham, Nicolai Cramer
Chem. Eur. J., January 11, 2016, DOI: 10.1002/chem.201504998. Read article.

Dehydrogenative Homocoupling of Alkyl Chains on Cu(110)

Dehydrogenative Homocoupling of Alkyl Chains on Cu(110)

Chains linked: Through the interplay of high-resolution scanning tunneling microscopy imaging and density functional theory calculations, the stepwise homocoupling of alkyl chains on Cu(110) is demonstrated, proceeding from the intact chain, via the dehydrogenative intermediates, to the final coupling products.

[Communication]
Liangliang Cai, Qiang Sun, Chi Zhang, Yuanqi Ding, Wei Xu
Chem. Eur. J., January 8, 2016, DOI: 10.1002/chem.201504152. Read article.

Copper-Catalyzed 8-Amido Chelation-Induced Remote C-H Amination of Quinolines

Copper-Catalyzed 8-Amido Chelation-Induced Remote C-H Amination of Quinolines

Access the inaccessible: A copper-catalyzed 8-amide chelation-induced remote C-H amination of quinolines has been developed (see scheme). This direct amination with readily available azodicarboxylates proceeded with perfect C5-regioselectivity offering amino-substituted 8-aminoquinolines in high yields (up to 96 %).

[Communication]
Harekrishna Sahoo, Mallu Kesava Reddy, Isai Ramakrishna, Mahiuddin Baidya
Chem. Eur. J., January 7, 2016, DOI: 10.1002/chem.201504207. Read article.

Origin of the Ability of α-Fe2O3 Mesopores to Activate C-H Bonds in Methane

Origin of the Ability of α-Fe2O3 Mesopores to Activate C-H Bonds in Methane

Origin of the activation: The inner surface structures of the pore wall in mesoporous α-Fe2O3 are mainly comprised of turbostratic ribbons and K crystal faces. They show excellent catalytic performance for methane activation, during which the C-H bonds are converted into C-O bonds in an O2 atmosphere at 140 °C (see figure).

[Full Paper]
Bing Dong, Zhen Han, Yongbo Zhang, Youyi Yu, Aiguo Kong, Yongkui Shan
Chem. Eur. J., January 7, 2016, DOI: 10.1002/chem.201503183. Read article.

Single-Component Phosphinous Acid Ruthenium(II) Catalysts for Versatile C-H Activation by Metal–Ligand Cooperation

Single-Component Phosphinous Acid Ruthenium(II) Catalysts for Versatile C-H Activation by Metal–Ligand Cooperation

A blockbuster catalyst: Well-defined ruthenium(II) phosphinous acid (PA) complexes were identified as powerful catalysts for highly selective C-H arylations with ample scope, which enabled low catalyst loadings and gave step-economical access to blockbuster drugs. Mechanistic studies were supportive of a PA-assisted C-H activation.

[Communication]
Daniel Zell, Svenja Warratz, Dmitri Gelman, Simon J. Garden, Lutz Ackermann
Chem. Eur. J., December 22, 2015, DOI: 10.1002/chem.201504851. Read article.

Chemo- and Regioselective Ethynylation of Tryptophan-Containing Peptides and Proteins

Chemo- and Regioselective Ethynylation of Tryptophan-Containing Peptides and Proteins

Alkynes on a gold Tr(i)p! Various peptides and one model protein were functionalized with ethynyl moieties at their tryptophan residues using Waser’s reagent, TIPS-EBX, under gold(I) catalysis (see scheme; TIPS=triisopropylsilyl). The reaction proceeded in a regio- and chemoselective manner leading to C2 substitution at the tryptophan residues only. Subsequently, the terminal alkyne was used to label one of the model peptides with a fluorophore by means of copper-catalyzed click chemistry.

[Communication]
Morten Borre Hansen, František Hubálek, Troels Skrydstrup, Thomas Hoeg-Jensen
Chem. Eur. J., December 22, 2015, DOI: 10.1002/chem.201504462. Read article.

Direct Synthesis of Protoberberine Alkaloids by Rh-Catalyzed C-H Bond Activation as the Key Step

Direct Synthesis of Protoberberine Alkaloids by Rh-Catalyzed C-H Bond Activation as the Key Step

Rhoad to alkaloids! A Rh-catalyzed intramolecular C-H bond activation/annulation of aldehydes and alkyne–amines provides a novel efficient method for the synthesis of various protoberberine salts and natural products in high yield under mild reaction conditions.

[Full Paper]
Jayachandran Jayakumar, Chien-Hong Cheng
Chem. Eur. J., December 22, 2015, DOI: 10.1002/chem.201504378. Read article.

Chelation-Assisted Nickel-Catalyzed Oxidative Annulation via Double C-H Activation/Alkyne Insertion Reaction

Chelation-Assisted Nickel-Catalyzed Oxidative Annulation via Double C-H Activation/Alkyne Insertion Reaction

In two shakes: Oxidative annulation by double C-H activation/alkyne insertion reaction was achieved by a nickel/NHC system. A Ni0/NiII catalytic cycle is proposed as the main catalytic cycle. The alkyne plays a double role as a two-component coupling partner and as a hydrogen acceptor.

[Full Paper]
Luis C. Misal Castro, Atsushi Obata, Yoshinori Aihara, Naoto Chatani
Chem. Eur. J., December 21, 2015, DOI: 10.1002/chem.201504596. Read article.

1,1,1,3,3,3-Hexafluoroisopropanol as a Remarkable Medium for Atroposelective Sulfoxide-Directed Fujiwara–Moritani Reaction with Acrylates and Styrenes

1,1,1,3,3,3-Hexafluoroisopropanol as a Remarkable Medium for Atroposelective Sulfoxide-Directed Fujiwara–Moritani Reaction with Acrylates and Styrenes

Influential solvent: Efficient access to atropo-enantioenriched biaryl moieties through asymmetric direct C-H activation, by using enantiopure sulfoxide as both the directing group and chiral auxiliary, is reported (see scheme). The key role of 1,1,1,3,3,3-hexafluoropropanol (HFIP) solvent is investigated.

[Full Paper]
Quentin Dherbassy, Geoffrey Schwertz, Matthieu Chessé, Chinmoy Kumar Hazra, Joanna Wencel-Delord, Françoise Colobert
Chem. Eur. J., December 18, 2015, DOI: 10.1002/chem.201503650. Read article.

Activation and Transformation of Ethane by Au2VO3+ Clusters with Closed-Shell Electronic Structures

Activation and Transformation of Ethane by Au2VO3+ Clusters with Closed-Shell Electronic Structures

The crucial role of gold in the transformation of ethane to ethene and dihydrogen is observed in the reaction between C2H6 and Au2VO3+ clusters with closed-shell electronic structures. The first C-H activation is initiated by gold rather than an oxygen species. The Au-Au dimer formed during the reactions plays important roles in converting ethane into ethene and making dihydrogen energetically more favorable.

[Full Paper]
Ya-Ke Li, Zi-Yu Li, Yan-Xia Zhao, Qing-Yu Liu, Jing-Heng Meng, Sheng-Gui He
Chem. Eur. J., December 17, 2015, DOI: 10.1002/chem.201503676. Read article.

Rhodium-Catalyzed Intramolecular C-H Bond Activation with Triazoles: Preparation of Stereodefined Pyrrolidines and Other Related Cyclic Compounds

Rhodium-Catalyzed Intramolecular C-H Bond Activation with Triazoles: Preparation of Stereodefined Pyrrolidines and Other Related Cyclic Compounds

Three is a magic number: On treatment of triazoles with [Rh2(C7H15CO2)4], the rhodium catalyst plays three roles, denitrogenation, C-H bond activation, and stereoselective cyclization, providing a new method for heterocycle synthesis. Intramolecular C-H bond insertion takes place at the benzylic position to give pyrrolidines and related heterocycles in good yields.

[Communication]
Masato Senoo, Ayana Furukawa, Takeshi Hata, Hirokazu Urabe
Chem. Eur. J., December 14, 2015, DOI: 10.1002/chem.201503823. Read article.

Recent Progress in Dehydro(genative) Diels–Alder Reaction

Recent Progress in Dehydro(genative) Diels–Alder Reaction

DDAism: Dehydrogenative cycloadditions have attracted significant attention in synthetic chemistry. This Minireview highlights the recent efforts towards the development of dehydro or dehydrogenative Diels–Alder reactions to construct diverse aromatic compounds by a concerted pathway or a stepwise process.

[Minireview]
Wenbo Li, Liejin Zhou, Junliang Zhang
Chem. Eur. J., November 24, 2015, DOI: 10.1002/chem.201503571. Read article.

Selective Heterogeneous C-H Activation/Halogenation Reactions Catalyzed by Pd@MOF Nanocomposites

Selective Heterogeneous C-H Activation/Halogenation Reactions Catalyzed by Pd@MOF Nanocomposites

A directed heterogeneous C-H activation/halogenation reaction catalyzed by readily synthesized Pd@MOF nanocatalysts was developed (see scheme). The heterogeneous Pd catalysts used were a novel and environmentally benign Fe-based metal–organic framework (MOF) (Pd@MIL-88B-NH2(Fe)) and the previously developed Pd@MIL-101-NH2(Cr). Very high conversions and selectivities were achieved under very mild reaction conditions and in short reaction times.

[Full Paper]
Vlad Pascanu, Fabian Carson, Marta Vico Solano, Jie Su, Xiaodong Zou, Magnus J. Johansson, Belén Martín-Matute
Chem. Eur. J., October 20, 2015, DOI: 10.1002/chem.201502918. Read article.

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