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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

Transient-Ligand-Enabled ortho-Arylation of Five-Membered Heterocycles: Facile Access to Mechanochromic Materials

Transient‐Ligand‐Enabled ortho‐Arylation of Five‐Membered Heterocycles: Facile Access to Mechanochromic Materials

Color shifters: The direct arylation of heteroarenes by a transient-ligand-directed strategy has been developed, without the need to construct and deconstruct the directing group. The route provides an opportunity to rapidly access novel mechanofluorochromic materials.

[Communication]
Bijin Li, Kapileswar Seth, Ben Niu, Lei Pan, Huiwen Yang, Haibo Ge
Angew. Chem. Int. Ed., February 23, 2018, https://doi.org/10.1002/anie.201713357 Read article

Selective Reductive Elimination at Alkyl Palladium(IV) by Dissociative Ligand Ionization: Catalytic C(sp3)−H Amination to Azetidines

Selective Reductive Elimination at Alkyl Palladium(IV) by Dissociative Ligand Ionization: Catalytic C(sp3)−H Amination to Azetidines

Crucial combo: A PdII-catalyzed γ-C−H amination of cyclic alkyl amines delivers highly substituted azetidines. The use of a benziodoxole tosylate oxidant in combination with AgOAc was crucial for controlling the selective reductive elimination pathway to the azetidines. The process is tolerant of a range of functional groups, including structural features derived from chiral α-amino alcohols, and leads to the diastereoselective formation of enantiopure azetidines.

[Communication]
Manuel Nappi, Chuan He, William G. Whitehurst, Ben G. N. Chappell, Matthew J. Gaunt
Angew. Chem. Int. Ed., February 22, 2018, https://doi.org/10.1002/anie.201800519 Read article

Palladium-Catalyzed Regioselective Aromatic Extension of Internal Alkynes through a Norbornene-Controlled Reaction Sequence

Palladium‐Catalyzed Regioselective Aromatic Extension of Internal Alkynes through a Norbornene‐Controlled Reaction Sequence

The right way round: A regioselective multicomponent reaction of aryl halides, 2-haloarylcarboxylic acids, and disubstituted acetylenes proceeds through C−H activation, decarboxylation, and annulation to give poly(hetero)aromatic compounds by aromatic extension. Alkyne carbopalladation is the last step of this tandem reaction.

[Communication]
Qingyang Zhao, Wai Chung Fu, Fuk Yee Kwong
Angew. Chem. Int. Ed., February 22, 2018, https://doi.org/10.1002/anie.201713207 Read article

Mechanistic DFT Study on Rhodium(III)-Catalyzed Double C−H Activation for Oxidative Annulations of 2-Substituted Imidazoles and Alkynes

Mechanistic DFT Study on Rhodium(III)‐Catalyzed Double C−H Activation for Oxidative Annulations of 2‐Substituted Imidazoles and Alkynes

Help not required! An interesting example of directing-group-free Cp*RhIII-catalyzed C(sp2)−H bond activation was revealed by a DFT study on RhIII-catalyzed oxidative annulations of 2-substituted imidazoles and alkynes. The experimental observations with different imidazole derivatives were explained well by the theoretical calculations.

[Full Paper]
Peipei Xie, Mengmeng Jia, Xiao-Hua Xu, Fan Chen, Yuanzhi Xia
Asian J. Org. Chem., February 22, 2018, https://doi.org/10.1002/ajoc.201700625 Read article

Arene-Ligand-Free Ruthenium(II/III) Manifold for meta-C−H Alkylation: Remote Purine Diversification

Arene‐Ligand‐Free Ruthenium(II/III) Manifold for meta‐C−H Alkylation: Remote Purine Diversification

Pur(in)e remote: meta-C−H alkylations were accomplished on sensitive purine nucleosides by an arene-ligand-free ruthenium catalyst with ample scope.

[Communication]
Fernando Fumagalli, Svenja Warratz, Shou-Kun Zhang, Torben Rogge, Cuiju Zhu, A. Claudia Stückl, Lutz Ackermann
Chem. Eur. J., February 21, 2018, https://doi.org/10.1002/chem.201800530 Read article

Transition-Metal-Free Cross-Dehydrogenative Coupling of Ethyl Arylacetates with Benzoic/Cinnamic Acids: A Practical Synthesis of α-Acyloxy Esters

Transition‐Metal‐Free Cross‐Dehydrogenative Coupling of Ethyl Arylacetates with Benzoic/Cinnamic Acids: A Practical Synthesis of α‐Acyloxy Esters

Cinnamon challenge: An efficient cross-dehydrogenative coupling of benzylic C(sp3)−H of ethyl arylacetates with benzoic/cinnamic acids has been developed to afford α-acyloxy esters in reasonably high yields under environmentally benign conditions.

[Communication]
Anup Kumar Sharma, Promod Kumar, Ramesh Kumar Vishwakarma, Krishna Nand Singh
Asian J. Org. Chem., February 21, 2018, https://doi.org/10.1002/ajoc.201800029 Read article

Ce1−xCrxO2−δ Nanocrystals as Efficient Catalysts for the Selective Oxidation of Cyclohexane to KA Oil at Low Temperature under Ambient Pressure

Ce1−xCrxO2−δ Nanocrystals as Efficient Catalysts for the Selective Oxidation of Cyclohexane to KA Oil at Low Temperature under Ambient Pressure

Perfect pair: Ce0.7Cr0.3O2−δ is highly active for the selective oxidation of cyclohexane to KA oil using H2O2 as an oxidant at low temperature. The CeO2 support stabilizes the Cr species in the lattice structure and promotes the catalytic activity of the Cr species.

[Full Paper]
Xiubing Huang, Guixia Zhao, Peng Wang, Haiyan Zheng, Wenjun Dong, Ge Wang
ChemCatChem, February 19, 2018, https://doi.org/10.1002/cctc.201701762 Read article

C–O Bonds from Pd-Catalyzed C(sp3)–H Reactions Mediated by Heteroatomic Groups

C–O Bonds from Pd‐Catalyzed C(sp3)–H Reactions Mediated by Heteroatomic Groups

[Microreview]
Jean Le Bras, Jacques Muzart
Eur. J. Org. Chem., February 14, 2018, https://doi.org/10.1002/ejoc.201701446 Read article

Synthesis of Functionalized (η5-Indenyl)rhodium(III) Complexes and Their Application to C−H Bond Functionalization

Synthesis of Functionalized (η5‐Indenyl)rhodium(III) Complexes and Their Application to C−H Bond Functionalization

Rh(o) in de Nile: It has been established that reductive complexation of functionalized benzofulvenes, prepared from commercially available indene derivatives, with RhCl3 in ethanol affords the corresponding indenyl–rhodium(III) dichlorides with various combinations of substituents. The indenyl–rhodium(III) complexes with one ethoxycarbonyl group showed high thermal stability and regioselectivity toward the oxidative [3+2] annulation of acetanilides with alkynes.

[Communication]
Jyunichi Terasawa, Yu Shibata, Yuki Kimura, Ken Tanaka
Chem. Asian J., February 01, 2018, https://doi.org/10.1002/asia.201701716 Read article

Silver-Catalyzed Efficient Synthesis of Oxindoles and Pyrroloindolines via α-Aminoalkylation of N-Arylacrylamides with Amino Acid Derivatives

Silver‐Catalyzed Efficient Synthesis of Oxindoles and Pyrroloindolines via α‐Aminoalkylation of N‐Arylacrylamides with Amino Acid Derivatives

Benefits of amino acids: α-Aminoalkylation of N-arylacrylamides with amino acid derivatives was achieved by silver-catalysis in moderate to high yields. The reaction provides an efficient strategy for the synthesis of functionalized oxindoles, and is suitable for a wide range of N-arylacrylamides and amino acids, both of which are inexpensive and readily available. The utility of the obtained oxindoles is demonstrated by a facile deprotection/cyclization synthesis of densely functionalized pyrroloindolines in moderate to high yields.

[Communication]
Kyalo Stephen Kanyiva, Sohei Makino, Takanori Shibata
Chem. Asian J., January 23, 2018, https://doi.org/10.1002/asia.201701739 Read article

Manganese-Catalyzed C−H Cyanation of Arenes with N-Cyano-N-(4-methoxy)phenyl-p-toluenesulfonamide

Manganese‐Catalyzed C−H Cyanation of Arenes with N‐Cyano‐N‐(4‐methoxy)phenyl‐p‐toluenesulfonamide

Almonds, anyone? The synthesis of aromatic nitriles through manganese-catalyzed C−H cyanation reactions of arenes with N-cyano-N-(4-methoxy)phenyl-p-toluenesulfonamide is described.

[Communication]
Xiaoqiang Yu, Jingjing Tang, Xinxin Jin, Yoshinori Yamamoto, Ming Bao
Asian J. Org. Chem., January 08, 2018, https://doi.org/10.1002/ajoc.201700628 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

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

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