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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

Iridium(III)-Catalyzed Regioselective Intermolecular Unactivated Secondary Csp3−H Bond Amidation

Iridium(III)‐Catalyzed Regioselective Intermolecular Unactivated Secondary Csp3−H Bond Amidation

Regioselective intermolecular sulfonylamidation of unactivated secondary C(sp3)−H bonds has been achieved using IrIII catalysts. N,N′-bichelating ligand plays a crucial role in enabling iridium nitrene insertion into secondary C(sp3)−H bonds via an outer-sphere pathway. This method tolerates a broad range of linear and branched-chain N-alkylamides, and provides efficient access to diverse γ-sulfonamido-substituted aliphatic amines.

[Communication]
Xinsheng Xiao, Cheng Hou, Zhenhui Zhang, Zhuofeng Ke, Jianyong Lan, Huanfeng Jiang, Wei Zeng
Angew. Chem. Int. Ed., August 26, 2016, DOI: 10.1002/anie.201606531. Read article

Ruthenium(II)-Catalyzed C−H Activation of Imidamides and Divergent Couplings with Diazo Compounds: Substrate-Controlled Synthesis of Indoles and 3H-Indoles

Ruthenium(II)‐Catalyzed C−H Activation of Imidamides and Divergent Couplings with Diazo Compounds: Substrate‐Controlled Synthesis of Indoles and 3H‐Indoles

Which way to go: NH indoles and 3H-indoles were synthesized by ruthenium(II)-catalyzed C−H activation of imidamides and intermolecular coupling with diazo compounds under mild conditions. The coupling of α-diazoketoesters afforded NH indoles by cleavage of the C(N2)−C(acyl) bond whereas α-diazomalonates gave 3H-indoles by C=N bond cleavage.

[Communication]
Yunyun Li, Zisong Qi, He Wang, Xifa Yang, Xingwei Li
Angew. Chem. Int. Ed., August 25, 2016, DOI: 10.1002/anie.201606316. Read article

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions

Under high pressure, the C≡N bond of acetonitrile is expected to polymerize into conjugated C=N bonds. It is however shown that when compressing CH3CN at 25 GPa, a hydrogen atom transfers along the −H2C−H⋅⋅⋅NC− hydrogen bond, which triggers the polymerization to form a dimer, 1D chain, and 2D nanoribbon. Finally, it converts into a graphitic polymer accompanied by the release of ammonia.

[Communication]
Haiyan Zheng, Kuo Li, George D. Cody, Christopher A. Tulk, Xiao Dong, Guoying Gao, Jamie J. Molaison, Zhenxian Liu, Mikhail Feygenson, Wenge Yang, Ilia N. Ivanov, Leonardo Basile, Juan-Carlos Idrobo, Malcolm Guthrie, Ho-kwang Mao
Angew. Chem. Int. Ed., August 25, 2016, DOI: 10.1002/anie.201606198. Read article

Visible-Light Photocatalytic Aerobic Benzylic C(sp3)−H Oxygenations with the 3DDQ*/tert-Butyl Nitrite Co-catalytic System

Visible‐Light Photocatalytic Aerobic Benzylic C(sp3)−H Oxygenations with the 3DDQ*/tert‐Butyl Nitrite Co‐catalytic System

DDQ can do: Visible-light-induced aerobic C(sp3)−H oxygenations of benzylic substrates are efficiently performed by using a co-catalytic system of 3DDQ* (DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone) and tert-butyl nitrite. The photocatalytic method offers a dramatic increase in reaction rate compared to the thermal protocol.

[Communication]
Fabian Rusch, Jan-Christian Schober, Malte Brasholz
ChemCatChem, August 22, 2016, DOI: 10.1002/cctc.201600704. 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

Selective Phenol Production by Hydrothermal Dehydrogenation of Cyclohexanone over Pd/C without External Oxygen and Hydrogen

Selective Phenol Production by Hydrothermal Dehydrogenation of Cyclohexanone over Pd/C without External Oxygen and Hydrogen

An efficient method for the hydrothermal dehydrogenation of cyclohexanone to phenol using recyclable Pd/C catalyst without external O2 and H2 was first reported. Pd/C as catalyst exhibited excellent catalytic performance and hydrothermal stability for the present transformation, and phenol was produced from cyclohexanone in 60.4 % yield with 100 % selectivity. TON of 8.27 and TOF of 3.31 h−1 were achieved.

[Full Paper]
Zhiyuan Song, Dezhang Ren, Jun Fu, Yunjie Liu, Tian Wang, Fangming Jin, Zhibao Huo
ChemistrySelect, July 22, 2016, DOI: 10.1002/slct.201600527. Read article

High-Valent Iron-Oxo and -Nitrido Complexes: Bonding and Reactivity

High‐Valent Iron‐Oxo and ‐Nitrido Complexes: Bonding and Reactivity

[Review]
Bhaskar Mondal, Lisa Roy, Frank Neese, Shengfa Ye
Isr. J. Chem., July 19, 2016, DOI: 10.1002/ijch.201600028. Read article

Cobalt-Catalyzed C-H Functionalizations by Imidate Assistance with Aryl and Alkyl Chlorides

Cobalt-Catalyzed C-H Functionalizations by Imidate Assistance with Aryl and Alkyl Chlorides

[Full Paper]
Ruhuai Mei, Lutz Ackermann
Adv. Synth. Catal., July 8, 2016, DOI: 10.1002/adsc.201600384. Read article.

RhIII-Catalyzed Directed C−H Bromination and Iodination to Synthesize Atropisomeric Biaryls

RhIII‐Catalyzed Directed C−H Bromination and Iodination to Synthesize Atropisomeric Biaryls

Not half biaryls: The highly efficient [RhIIICp*]-catalyzed directed C-H bromination and iodination reaction of 2-aryl isoquinolines/pyridines affords atropisomeric biaryl compounds in good yields.

[Communication]
Kiseong Kim, Jaeyong Hyun, Jin Kim, Hyunwoo Kim
Asian J. Org. Chem., July 08, 2016, DOI: 10.1002/ajoc.201600259. Read article

Palladium-Catalyzed Oxidative Carbonylation of Aromatic C-H Bonds with Alcohols using Molybdenum Hexacarbonyl as the Carbon Monoxide Source

Palladium-Catalyzed Oxidative Carbonylation of Aromatic C-H Bonds with Alcohols using Molybdenum Hexacarbonyl as the Carbon Monoxide Source

[Update]
Zechao Wang, Yahui Li, Fengxiang Zhu, Xiao-Feng Wu
Adv. Synth. Catal., June 15, 2016, DOI: 10.1002/adsc.201600395. 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.

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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