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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

Mild Decarboxylative C−H Alkylation: Computational Insights for Solvent-Robust Ruthenium(II) Domino Manifold

Mild Decarboxylative C−H Alkylation: Computational Insights for Solvent‐Robust Ruthenium(II) Domino Manifold

Ex silico: Decarboxylative C−H alkylations were realized through key mechanistic insights, enabling ruthenium(II)-catalyzed domino C−H activation/decarboxylation under exceedingly mild conditions.

[Communication]
N. Y. Phani Kumar, Torben Rogge, Santhivardhana Reddy Yetra, Alexander Bechtoldt, Eric Clot, Lutz Ackermann
Chem. Eur. J., October 18, 2017, https://doi.org/10.1002/chem.201703680 Read article

Elemental-Sulfur-Promoted C(sp3)−H Activation of Methyl Heteroarenes Leading to Thioamides

Elemental‐Sulfur‐Promoted C(sp3)−H Activation of Methyl Heteroarenes Leading to Thioamides

Release Me2N(ight)! Sulfur-promoted C(sp3)−H activation of methyl heteroarenes generates bioactive thioamides. This transformation successfully furnished a series of heterocyclic thioamides with excellent yields and it could be conducted on gram scale with good reaction efficiency. Mechanistic studies showed that methyl heteroarenes reacted with dimethylamine released from DMF to form the desired thioamide.

[Communication]
Jianming Liu, Shanshan Zhao, Xuyang Yan, Yanyan Zhang, Shufang Zhao, Kelei Zhuo, Yuanyuan Yue
Asian J. Org. Chem., October 18, 2017, https://doi.org/10.1002/ajoc.201700532 Read article

RuII-Catalyzed ortho-Sulfonamidation of α-Tetralones with Sulfonyl Azides and Synthesis of Sivelestat by Aromatic C−H Activation

RuII‐Catalyzed ortho‐Sulfonamidation of α‐Tetralones with Sulfonyl Azides and Synthesis of Sivelestat by Aromatic C−H Activation

Amide other reactions: A method has been developed for the sulfonamidation of α-tetralones and 1,4-naphthoquinones by using sulfonyl azides and a RuII/AgI catalytic system (see scheme; DCE=1,2-dichloroethane). Tetralones underwent C−H bond functionalization exclusively at the ortho position, whereas 1,4-addition was the primary reaction for 1,4-naphthoquinone. This highly regioselective approach was also used to synthesize sivelestat, an inhibitor of human neutrophil elastase.

[Full Paper]
Medikonda V. Krishna Rao, Keesari Nagarjuna Reddy, Balasubramaniam Sridhar, Basi V. Subba Reddy
Asian J. Org. Chem., October 18, 2017, https://doi.org/10.1002/ajoc.201700356 Read article

η1-Arene Complexes as Intermediates in the Preparation of Molecular Phosphorescent Iridium(III) Complexes

η1‐Arene Complexes as Intermediates in the Preparation of Molecular Phosphorescent Iridium(III) Complexes

Green phosphorescence: Molecular phosphorescent heteroleptic bis-tridentate iridium(III) complexes with a six-membered heterometallacycle in their structure (see figure) have been prepared via η1-arene intermediates. They are green emitters that display short lifetimes (110 μs) and high quantum yields (0.73–0.87) in the solid state.

[Full Paper]
Miguel A. Esteruelas, Daniel Gómez-Bautista, Ana M. López, Enrique Oñate, Jui-Yi Tsai, Chuanjun Xia
Chem. Eur. J., October 16, 2017, https://doi.org/10.1002/chem.201703252 Read article

Asymmetric Cycloisomerization of o-Alkenyl-N-Methylanilines to Indolines by Iridium-Catalyzed C(sp3)−H Addition to Carbon–Carbon Double Bonds

Asymmetric Cycloisomerization of o‐Alkenyl‐N‐Methylanilines to Indolines by Iridium‐Catalyzed C(sp3)−H Addition to Carbon–Carbon Double Bonds

Build a bridge: Highly enantioselective cycloisomerization of N-methylanilines, bearing o-alkenyl groups, into indolines was established. An iridium catalyst bearing a bidentate chiral diphosphine effectively promotes the intramolecular addition of the C(sp3)−H bond across a C=C bond in an enantioselective fashion. The reaction gives indolines bearing a quaternary stereogenic carbon center at the 3-position.

[Communication]
Takeru Torigoe, Toshimichi Ohmura, Michinori Suginome
Angew. Chem. Int. Ed., October 16, 2017, https://doi.org/10.1002/anie.201708578 Read article

Rhodium(III)-Catalyzed Directed C−H Amidation of N-Nitrosoanilines and Subsequent Formation of 1,2-Disubstituted Benzimidazoles

Rhodium(III)‐Catalyzed Directed C−H Amidation of N‐Nitrosoanilines and Subsequent Formation of 1,2‐Disubstituted Benzimidazoles

Can't say NO to that! An efficient rhodium-catalyzed direct C−H amidation of N-nitrosoanilines with 1,4,2-dioxazol-5-ones as amidating agents and subsequent formation of 1,2-disubstituted benzimidazoles via a one-pot reaction has been developed.

[Communication]
Yanyu Chen, Rong Zhang, Qiujun Peng, Lanting Xu, XianHua Pan
Chem. Asian J., October 12, 2017, https://doi.org/10.1002/asia.201701287 Read article

Arylation of Aniline C(sp3)−H Bonds with Phenols via an In Situ Activation Strategy

Arylation of Aniline C(sp3)−H Bonds with Phenols via an In Situ Activation Strategy

A general and efficient arylation of aniline C(sp3)−H bonds with phenols has been achieved by an in situ activation strategy via visible-light photoredox/nickel dual catalysis. This protocol directly uses phenols as proelectrophiles and features high step-efficiency, time-economy, environmental impact, broad substrate scope, high yields, good functional-group tolerance, and low catalyst loading.

[Communication]
Yong-Yuan Gui, Zi-Xiao Wang, Wen-Jun Zhou, Li-Li Liao, Lei Song, Zhu-Bao Yin, Jing Li, Da-Gang Yu
Asian J. Org. Chem., October 10, 2017, https://doi.org/10.1002/ajoc.201700450 Read article

Ligand-Assisted Heteroaryl C(sp2)−H Bond Activation by a Cationic Ruthenium(II) Complex for Alkenylation of Heteroarenes with Alkynes Directed by Biorelevant Heterocycles

Ligand‐Assisted Heteroaryl C(sp2)−H Bond Activation by a Cationic Ruthenium(II) Complex for Alkenylation of Heteroarenes with Alkynes Directed by Biorelevant Heterocycles

(Hetero)cycling there: Heteroaryl C(sp2)−H bond activation has been catalyzed by an in situ generated cationic RuII complex for alkenylation of heteroarenes with alkynes directed by biorelevant benzazoles. The reaction has broad scope with respect to the heteroarene (e.g., thiophene, furan, N-methyl pyrrole, and 3-indole) and the alkyne (symmetrical and unsymmetrical diaryl, dialkyl, aryl alkyl alkynes), affording high yields and with excellent chemo-, regio-, and stereoselectivity.

[Full Paper]
Bhavin V. Pipaliya, Asit K. Chakraborti
ChemCatChem, October 09, 2017, https://doi.org/10.1002/cctc.201701016 Read article

Novel Sulfonated CNN Pincer Ligands for Facile C−H Activation at a Pt(II) Center

Novel Sulfonated CNN Pincer Ligands for Facile C−H Activation at a Pt(II) Center

[Full Paper]
David Watts, Daoyong Wang, Peter Y. Zavalij, Andrei N. Vedernikov
Isr. J. Chem., October 06, 2017, https://doi.org/10.1002/ijch.201700063 Read article

Programmed Site-Selective Palladium-Catalyzed Arylation of Thieno[3,2-b]thiophene

Programmed Site‐Selective Palladium‐Catalyzed Arylation of Thieno[3,2‐b]thiophene

I C3 you C5: Mono-, di-, tri-, and tetraarylated thieno[3,2-b]thiophenes are synthesized by direct site-selective Pd-catalyzed C−H activation reactions with various aryl bromides in the presence of a phosphine-free Pd(OAc)2/KOAc catalyst system in N,N-dimethylacetamide (DMAc). The arylation takes place at the C-3 or C-5 position in the thieno[3,2-b]thiophene skeleton depending on the nature and size of the 2-aryl substituent.

[Full Paper]
T. M. Ha Vuong, Didier Villemin, Hung-Huy Nguyen, Tin Thanh Le, Tung T. Dang, Hien Nguyen
Chem. Asian J., October 02, 2017, https://doi.org/10.1002/asia.201700562 Read article

Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria–Zirconia Catalysts in a Single Reactor

Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria–Zirconia Catalysts in a Single Reactor

Controlled oxidation: Methanol and ethanol are produced continuously from methane and oxygen in a single reaction over a catalyst consisting of NiO clusters on ceria–zirconia. Oxygen is the abundantly available oxidant for this reaction and the presence of steam ensures the production of alcohols as opposed to products of the complete combustion of methane.

[Communication]
Chukwuemeka Okolie, Yasmeen F. Belhseine, Yimeng Lyu, Matthew M. Yung, Mark H. Engelhard, Libor Kovarik, Eli Stavitski, Carsten Sievers
Angew. Chem. Int. Ed., September 26, 2017, https://doi.org/10.1002/anie.201704704 Read article

Insights into Activation of Cobalt Pre-Catalysts for C(sp2)−H Functionalization

Insights into Activation of Cobalt Pre‐Catalysts for C(sp2)−H Functionalization

[Full Paper]
Jennifer V. Obligacion, Hongyu Zhong, Paul J. Chirik
Isr. J. Chem., September 25, 2017, https://doi.org/10.1002/ijch.201700072 Read article

A DFT Survey of the Effects of d-Electron Count and Metal Identity on the Activation and Functionalization of C−H Bonds for Mid to Late Transition Metals

A DFT Survey of the Effects of d‐Electron Count and Metal Identity on the Activation and Functionalization of C−H Bonds for Mid to Late Transition Metals

[Full Paper]
Catherine A. Moulder, Thomas R. Cundari
Isr. J. Chem., September 21, 2017, https://doi.org/10.1002/ijch.201700066 Read article

Nickel-Catalyzed Benzylation of C−H Bonds in Aromatic Amides with Benzyltrimethylammonium Halides

Nickel‐Catalyzed Benzylation of C−H Bonds in Aromatic Amides with Benzyltrimethylammonium Halides

[Communication]
Akane Sasagawa, Mao Yamaguchi, Yusuke Ano, Naoto Chatani
Isr. J. Chem., September 19, 2017, https://doi.org/10.1002/ijch.201700044 Read article

C–H Bond Activation and Isoprene Polymerization by Lutetium Alkylaluminate/gallate Complexes Bearing a Peripheral Boryl and a Bulky Hydrotris(pyrazolyl)borate Ligand

C–H Bond Activation and Isoprene Polymerization by Lutetium Alkylaluminate/gallate Complexes Bearing a Peripheral Boryl and a Bulky Hydrotris(pyrazolyl)borate Ligand

The addition compound A obtained from terminal methyl complex [(TptBu,Me)LuMe2] and organoaluminum boryl compound [Me2Al{B(NDippCH)2}] engages in thermolytic C–H bond activation to afford complex B; cationized B (shown to the left as B′) polymerizes isoprene, possibly via a Lu–CH2(R)–Al linkage as the initiating site.

[Full Paper]
Martin Bonath, Christoph O. Hollfelder, Dorothea Schädle, Cäcilia Maichle-Mössmer, Peter Sirsch, Reiner Anwander
Eur. J. Inorg. Chem., September 15, 2017, https://doi.org/10.1002/ejic.201700730 Read article

An Efficient Synthesis of Pyrrolo[1,2-a]quinoxalines by Copper-Catalyzed C−H Activation of Arylacetic Acids

An Efficient Synthesis of Pyrrolo[1,2‐a]quinoxalines by Copper‐Catalyzed C−H Activation of Arylacetic Acids

Copper-catalyzed cascade protocol for the synthesis of pyrrolo[1,2-a]quinoxaline is reported through C−H activation of arylacetic acids under O2 atmosphere. The remarkable features of this protocol are the use of easily available starting materials, cheap catalyst, wide functional group tolerance and good to excellent yields of the products.

[Communication]
Jatin J. Lade, Bhausaheb N. Patil, Mahendra V. Vhatkar, Kamlesh S. Vadagaonkar, Atul C. Chaskar
Asian J. Org. Chem., September 05, 2017, https://doi.org/10.1002/ajoc.201700239 Read article

Synthesis and Anticancer Evaluation of 2,3-Disubstituted Indoles Derived from Azobenzenes and Internal Olefins

Synthesis and Anticancer Evaluation of 2,3‐Disubstituted Indoles Derived from Azobenzenes and Internal Olefins

Azo-directed rhodium(III)-catalysed C–H functionalization and intramolecular annulation reactions between azobenzenes and internal olefins are described. The resulting indoles were evaluated for in-vitro anticancer activity against various human cancer cell lines.

[Full Paper]
Yongguk Oh, Sang Hoon Han, Neeraj Kumar Mishra, Umasankar De, Junho Lee, Hyung Sik Kim, Young Hoon Jung, In Su Kim
Eur. J. Org. Chem., September 01, 2017, https://doi.org/10.1002/ejoc.201701001 Read article

Cu(TFA)2-Catalyzed Picolinamido-Directed C(sp2)−H Cyanation of Naphthalenes by Using Benzoyl Cyanide as a Cyano Source

Cu(TFA)2‐Catalyzed Picolinamido‐Directed C(sp2)−H Cyanation of Naphthalenes by Using Benzoyl Cyanide as a Cyano Source

Pick-a-little/Talk-a-little: A method for the Cu(TFA)2-catalyzed (TFA=trifluoroacetic acid) picolinamido-directed C8−H cyanation of naphthalene derivatives with benzoyl cyanide as the cyano source has been developed. We prepared a total of 22 products, 10 of which have not previously been reported. Benzoyl cyanide was originally employed for the C(sp2)−H cyanation of arenes. TFA=trifluoroacetic acid and DMAc=N,N-dimethylacetamide.

[Full Paper]
He Song, Xiaochong Liu, Chenglong Wang, Jingyi Qiao, Wenyi Chu, Zhizhong Sun
Asian J. Org. Chem., August 31, 2017, https://doi.org/10.1002/ajoc.201700418 Read article

Copper-Catalyzed C−H Activation of Substituted Pyridines Leading to Imidazopyridine Derivatives via Self-Redox of the Substrates

Copper‐Catalyzed C−H Activation of Substituted Pyridines Leading to Imidazopyridine Derivatives via Self‐Redox of the Substrates

High self-esteem: A simple and practical copper-catalyzed C−H activation of substituted pyridines with O-aryl oximes leading to imidazo[1,2-a]pyridines has been developed via self-redox of the substrates. The imidazo[1,2-a]pyridine derivatives were prepared in moderate to good yields. Interestingly, the C−H activation did not need an added oxidant, additive, acid or base. Therefore, the present method provides a good strategy for the synthesis of N-heterocycles.

[Communication]
Zhenbang Lou, Haijun Yang, Changjin Zhu, Hua Fu
Asian J. Org. Chem., August 25, 2017, https://doi.org/10.1002/ajoc.201700381 Read article

Activation, Deactivation and Reversibility in a Series of Homogeneous Iridium Dehydrogenation Catalysts

Activation, Deactivation and Reversibility in a Series of Homogeneous Iridium Dehydrogenation Catalysts

[Review]
Liam S. Sharninghausen, Robert H. Crabtree
Isr. J. Chem., August 10, 2017, https://doi.org/10.1002/ijch.201700048 Read article

Synthesis of Benzopyrans by Enolate-Directed Rhodium-Catalyzed Oxidative C−H Alkenylation of 1,3-Dicarbonyl Compounds

Synthesis of Benzopyrans by Enolate‐Directed Rhodium‐Catalyzed Oxidative C−H Alkenylation of 1,3‐Dicarbonyl Compounds

Celebrating diversity: 2-Aryl-1,3-dicarbonyl compounds are shown to be reactive in enolate-directed oxidative alkenylations for the synthesis of benzopyrans in good to excellent yields. Coupling of a diverse range of substrates to a variety of electron-deficient alkenes was efficiently achieved by rhodium catalysis. Furthermore, the scope of the reaction was broad with good functional group tolerance.

[Full Paper]
Hari Babu Bollikolla, Subrahmanyam Choppakatla, Naresh Polam, Vijaya Durga Thripuram, Suresh Reddy Chidipudi
Asian J. Org. Chem., August 09, 2017, https://doi.org/10.1002/ajoc.201700371 Read article

Iridium Halide Complexes [1,1-X2-8-SMe2-1,2,8-IrC2B9H10]2 (X = Cl, Br, I): Synthesis, Reactivity and Catalytic Activity

Iridium Halide Complexes [1,1‐X2‐8‐SMe2‐1,2,8‐IrC2B9H10]2 (X = Cl, Br, I): Synthesis, Reactivity and Catalytic Activity

Iridium halide complexes [1,1-X2-8-SMe2-1,2,8-IrC2B9H10]2 (X = Cl, Br, I) were synthesized by reaction of the cyclooctadiene derivative 1-cod-8-SMe2-1,2,8-IrC2B9H10 with anhydrous hydrohalic acids HX. These complexes have proven to be effective catalysts for the dimerization of alkynes and the reductive amination of aldehydes and ketones.

[Full Paper]
Alexander P. Molotkov, Mikhail M. Vinogradov, Alexey P. Moskovets, Olga Chusova, Sergey V. Timofeev, Vasilii A. Fastovskiy, Yulia V. Nelyubina, Alexander A. Pavlov, Denis A. Chusov, Dmitry A. Loginov
Eur. J. Inorg. Chem., August 01, 2017, https://doi.org/10.1002/ejic.201700498 Read article

Iron-Catalyzed C−C Bond Formation via Chelation-Assisted C−H Activation

Iron‐Catalyzed C−C Bond Formation via Chelation‐Assisted C−H Activation

[Review]
Naohiko Yoshikai
Isr. J. Chem., July 26, 2017, https://doi.org/10.1002/ijch.201700047 Read article

Group 9 Transition Metal-Catalyzed C−H Halogenations

Group 9 Transition Metal‐Catalyzed C−H Halogenations

[Review]
Fabian Lied, Tuhin Patra, Frank Glorius
Isr. J. Chem., July 07, 2017, https://doi.org/10.1002/ijch.201700053 Read article

Synthesis and Biological Activity of Octaketides from the Cytosporone Family

Synthesis and Biological Activity of Octaketides from the Cytosporone Family

[Full Paper]
Max von Delius, Christine M. Le, Bernhard Ellinger, Maria Kuzikov, Sheraz Gul, Vy M. Dong
Isr. J. Chem., July 07, 2017, https://doi.org/10.1002/ijch.201700023 Read article

C–H Activation and Alkyne Annulation via Automatic or Intrinsic Directing Groups: Towards High Step Economy

C–H Activation and Alkyne Annulation via Automatic or Intrinsic Directing Groups: Towards High Step Economy

Express of direction: Directing group (DG) strategy is widely used for selective C–H functionalization. In this account, we described our efforts and recent advances focused on C–H activation and alkyne annulation. By using various automatic DGs (DGauto) and intrinsic DGs (DGin), diverse heterocycles and carbocycles can be obtained from simple building blocks or parent molecules with high step economy.

[Personal Account]
Liyao Zheng, Ruimao Hua
Chem. Rec., July 06, 2017, https://doi.org/10.1002/tcr.201700024 Read article

Convergent Synthesis of α-Branched Amines by Transition-Metal-Catalyzed C−H Bond Additions to Imines

Convergent Synthesis of α‐Branched Amines by Transition‐Metal‐Catalyzed C−H Bond Additions to Imines

[Review]
Joshua R. Hummel, Jonathan A. Ellman
Isr. J. Chem., June 29, 2017, https://doi.org/10.1002/ijch.201700021 Read article

Unexpected Solvent Effects in the Isomerization of iPrPCPIr(η2-PhC≡CPh) to a 1-Iridaindene

Unexpected Solvent Effects in the Isomerization of iPrPCPIr(η2‐PhC≡CPh) to a 1‐Iridaindene

[Full Paper]
Miles Wilklow-Marnell, William W. Brennessel, William D. Jones
Isr. J. Chem., June 14, 2017, https://doi.org/10.1002/ijch.201700013 Read article

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