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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

Cover Picture: Heterogeneous Chitosan@Copper(II)-Catalyzed Remote Trifluoromethylation of Aminoquinolines with the Langlois Reagent by Radical Cross-Coupling (ChemCatChem 23/2016)

Cover Picture: Heterogeneous Chitosan@Copper(II)‐Catalyzed Remote Trifluoromethylation of Aminoquinolines with the Langlois Reagent by Radical Cross‐Coupling (ChemCatChem 23/2016)

The Front Cover illustrates the first example of an heterogeneous catalyst Chitosan@Cu(OAc)2-catalyzed remote trifluoromethylation of aminoquinolines at C5 position under mild conditions.In their Communication, C. Shen et al. demonstrate that the trifluoromethylation products can be isolated in good to excellent yields using this method. Most importantly, the heterogeneous catalyst Chitosan@Cu(OAc)2 can been recycled many times without significant loss of catalytic performance. This protocol proves that the chitosan-based catalyst can further set the stage for the efficient reuse of the heterogeneous copper catalyst in position-selective C-H activations. More information can be found in the Communication by C. Shen et al. on page 3560 in Issue 23, 2016 (DOI: 10.1002/cctc.201601068).

[Cover Picture]
Chao Shen, Jun Xu, Beibei Ying, Pengfei Zhang
ChemCatChem, December 08, 2016, DOI: 10.1002/cctc.201601456. Read article

Ruthenium-Catalyzed C−H Arylation of Benzoic Acids and Indole Carboxylic Acids with Aryl Halides

Ruthenium‐Catalyzed C−H Arylation of Benzoic Acids and Indole Carboxylic Acids with Aryl Halides

Active near acid: The first Ru-catalyzed C−H arylation of benzoic acids with readily available aryl (pseudo)halides, allowing the arylation of previously challenging hindered benzoic acids and the use of generally unreactive ortho-substituted haloarenes. Furthermore, our new protocol can efficiently be applied to indole carboxylic acids, thus allowing access to C7-, C6-, C5- and C4-arylated indole compounds; a departure from the classical enhanced reactivity of C2 and C3 in indole.

[Communication]
Marco Simonetti, Diego M. Cannas, Adyasha Panigrahi, Szymon Kujawa, Michal Kryjewski, Pan Xie, Igor Larrosa
Chem. Eur. J., December 05, 2016, DOI: 10.1002/chem.201605068. Read article

Iron-Catalyzed Oxidative C−C and N−N Coupling of Diarylamines and Synthesis of Spiroacridines

Iron‐Catalyzed Oxidative C−C and N−N Coupling of Diarylamines and Synthesis of Spiroacridines

Let us count the ways… Catalysis by iron–hexadecafluorophthalocyanine enabled the aerobic coupling of diarylamines to form 2,2′-bis(arylamino)biaryl compounds, tetraarylhydrazines, or 5,6-dihydrobenzo[c]cinnolines. The chemoselectivity of these transformations was controlled by acid or base additives (see picture).

[Communication]
Raphael F. Fritsche, Gabriele Theumer, Olga Kataeva, Hans-Joachim Knölker
Angew. Chem. Int. Ed., December 05, 2016, DOI: 10.1002/anie.201610168. Read article

Palladium-Catalyzed C−H Functionalization of Phenyl 2-Pyridylsulfonates

Palladium‐Catalyzed C−H Functionalization of Phenyl 2‐Pyridylsulfonates

Phenols more than just great antioxidants: An efficient palladium-catalyzed ortho-alkenylation and acetoxylation of phenols is described. The reaction provides access to coumarins and benzofurans via a seven-membered cyclopalladated intermediate, showing complete regio- and diastereoselectivity.

[Full Paper]
Bin Li, Dong-Dong Guo, Shi-Huan Guo, Gao-Fei Pan, Ya-Ru Gao, Yong-Qiang Wang
Chem. Asian J., November 29, 2016, DOI: 10.1002/asia.201601413. Read article

Palladium-Catalyzed Acylation of Arenes by 1,2,3-Triazole-Directed C–H Activation

Palladium‐Catalyzed Acylation of Arenes by 1,2,3‐Triazole‐Directed C–H Activation

A facile method for the regioselective acylation of 1,4-disubstituted 1,2,3-triazoles by using a Pd-catalyzed C–H bond activation strategy with tert-butyl hydroperoxide (TBHP) as an oxidant and an aromatic aldehyde as the acyl source has been developed. This approach was applied to a wide range of substrates to generate various 1,2,3-triazole derivatives that have a diaryl ketone scaffold.

[Full Paper]
Fen Zhao, Zhen Chen, Yaowen Liu, Kai Xie, Yubo Jiang
Eur. J. Org. Chem., November 22, 2016, DOI: 10.1002/ejoc.201601061. Read article

Heterogeneous Chitosan@Copper(II)-Catalyzed Remote Trifluoromethylation of Aminoquinolines with the Langlois Reagent by Radical Cross-Coupling

Heterogeneous Chitosan@Copper(II)‐Catalyzed Remote Trifluoromethylation of Aminoquinolines with the Langlois Reagent by Radical Cross‐Coupling

A tri-ing method: The remote C−H trifluoromethylation of N-(quinolin-8-yl)benzamide derivatives is accomplished with a user-friendly chitosan-based heterogeneous copper catalyst, CS@Cu(OAc)2, under mild conditions. The coupling products are obtained in good to excellent yields, the catalyst shows good recyclability, and the low-costing stable Langlois reagent is used as the “CF3” source. A single-electron-transfer process is thought to be involved.

[Communication]
Chao Shen, Jun Xu, Beibei Ying, Pengfei Zhang
ChemCatChem, November 22, 2016, DOI: 10.1002/cctc.201601068. Read article

Copper(II)-Catalyzed Direct Azidation of N-Acylated 8-Aminoquinolines by Remote C−H Activation

Copper(II)‐Catalyzed Direct Azidation of N‐Acylated 8‐Aminoquinolines by Remote C−H Activation

Move azide: A simple and efficient method for the copper(II)-catalyzed C5 azidation of N-acylated 8-aminoquinolines by remote C−H activation is developed. On the basis of this reaction, C5-azidated 8-amidoquinolines are synthesized in moderate to good yields.

[Communication]
Yandong Dou, Zhenda Xie, Zongguo Sun, Hongli Fang, Chao Shen, Pengfei Zhang, Qing Zhu
ChemCatChem, November 15, 2016, DOI: 10.1002/cctc.201600874. Read article

Iridium(III)-Catalyzed Regioselective Carbenoid Insertion C–H Alkylation by α-Diazotized Meldrum's Acid

Iridium(III)‐Catalyzed Regioselective Carbenoid Insertion C–H Alkylation by α‐Diazotized Meldrum's Acid

[Communication]
Honggui Lv, William L. Xu, Kunhua Lin, Jingjing Shi, Wei Yi
Eur. J. Org. Chem., November 11, 2016, DOI: 10.1002/ejoc.201601212. Read article

Palladium-Catalyzed Oxidative Cyclization for the Synthesis of 2-Alkylimidazo[5,1,2-cd]indolizines

Palladium‐Catalyzed Oxidative Cyclization for the Synthesis of 2‐Alkylimidazo[5,1,2‐cd]indolizines

An effective palladium-catalyzed direct arylation of 2-alkyl-imidazo[1,2-a]pyridine with alkynes towards 2-alkyl-imidazo[5,1,2-cd]indolizines through double C–H functionalization was developed. The catalyst precursor is an ionic palladium(II) complex bearing amido-functionalized N-heterocyclic carbene and triphenylphosphine ligands.

[Full Paper]
Sanjay Kumar Ghosh, Debalina Ghosh, Ratnava Maitra, Ya-Ting Kuo, Hon Man Lee
Eur. J. Org. Chem., November 08, 2016, DOI: 10.1002/ejoc.201601019. Read article

C−H Activation of Methane to Formaldehyde on Ce1−xZrxO2 Thin Films: A Step to Bridge the Material Gap

C−H Activation of Methane to Formaldehyde on Ce1−xZrxO2 Thin Films: A Step to Bridge the Material Gap

Kiss me quick: The C−H activation of CH4 to HCHO is explored under technically relevant conditions on porous Ce-rich Ce1−xZrxO2 thin films with the aim to address the material gap and mechanistic aspects. The migration of electron-rich oxygen vacancy sites to the surface is responsible for HCHO formation. A short contact time and fast excursion between CH4- and O2-rich compositions could improve the HCHO selectivity further.

[Full Paper]
Anjani Dubey, Sadhu K. Kolekar, Chinnakonda S. Gopinath
ChemCatChem, November 07, 2016, DOI: 10.1002/cctc.201600670. Read article

Rhodium(III)-Catalysed Carbenoid C(sp2)–H Functionalisation of Aniline Substrates with α-Diazo Esters: Formation of Oxindoles and Characterisation/Utility of an Intermediate-Like Rhodacycle

Rhodium(III)‐Catalysed Carbenoid C(sp2)–H Functionalisation of Aniline Substrates with α‐Diazo Esters: Formation of Oxindoles and Characterisation/Utility of an Intermediate‐Like Rhodacycle

The RhIII-catalysed synthesis of 3-sulfonyloxindoles using 2-anilinopyridines and sulfonyl α-diazo esters is reported. Under similar conditions, ortho-alkylated 6-anilinopurine nucleobases/nucleosides were obtained by treating purine precursors with α-diazo esters. An intermediate-like rhodacycle, which is also an effective catalyst for these reactions, has been structurally characterised.

[Full Paper]
Srinivasarao Allu, Manjula Ravi, K. C. Kumara Swamy
Eur. J. Org. Chem., November 04, 2016, DOI: 10.1002/ejoc.201600968. Read article

Palladium-Catalyzed Domino Reaction of Two Aryl Iodides involving C–H Activation Processes: Efficient Synthesis of Fused Polycycles

Palladium‐Catalyzed Domino Reaction of Two Aryl Iodides involving C–H Activation Processes: Efficient Synthesis of Fused Polycycles

A palladium-catalyzed intermolecular domino reaction involving a sequence of C–H activations is reported. This reaction provides a simple and efficient method for the synthesis of fused polycycles from simple starting materials. cod = cyclooctadiene, NMP = 1-methylpyrrolidin-2-one, TBAB = tetrabutylammonium bromide.

[Communication]
Hai-Yu He, Wei Wang, Xiao-Jun Yu, Jin Huang, Lei Jian, Hai-Yan Fu, Xue-Li Zheng, Hua Chen, Rui-Xiang Li
Eur. J. Org. Chem., November 03, 2016, DOI: 10.1002/ejoc.201601051. Read article

Selective Borylation of [4]Helicene

Selective Borylation of [4]Helicene

The Ir-catalyzed borylation of [4]helicene has been studied. The monoborylation proceeds to give a mixture of 2- and 3-borylated products in good yields. The use of sterically demanding ligands favors the formation of the 3-borylated product. The monoborylated [4]helicenes were arylated by using a Suzuki–Miyaura cross-coupling reaction or oxidized to the corresponding phenols in very good yields.

[Full Paper]
David Nečas, Reinhard P. Kaiser, Jan Ulč
Eur. J. Org. Chem., October 27, 2016, DOI: 10.1002/ejoc.201600979. Read article

Mild Palladium Catalyzed ortho C-H Bond Functionalizations of Aniline Derivatives

Mild Palladium Catalyzed ortho C‐H Bond Functionalizations of Aniline Derivatives

In this account we summarize and discuss synthetic solutions for the realization of palladium catalyzed, ortho-directed C-H functionalization of aniline derivatives under mild reaction conditions for the construction of new carbon-carbon and carbon-oxygen bonds.

[Personal Account]
Orsolya Tischler, Balázs Tóth, Zoltán Novák
The Chemical Record, August 09, 2016, DOI: 10.1002/tcr.201600059. Read article

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