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1

Wencel-Delord, Joanna, and Françoise Colobert. "Asymmetric C(sp2)H Activation." Chemistry - A European Journal 19, no. 42 (2013): 14010–17. http://dx.doi.org/10.1002/chem.201302576.

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2

Wencel-Delord, Joanna, and Francoise Colobert. "ChemInform Abstract: Asymmetric C(sp2)-H Activation." ChemInform 45, no. 2 (2013): no. http://dx.doi.org/10.1002/chin.201402241.

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3

Bakthadoss, Manickam, Tadiparthi Thirupathi Reddy, Vishal Agarwal, and Duddu S. Sharada. "Ester-directed orthogonal dual C–H activation and ortho aryl C–H alkenylation via distal weak coordination." Chemical Communications 58, no. 9 (2022): 1406–9. http://dx.doi.org/10.1039/d1cc06097j.

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An orthogonal cross-coupling between aromatic C(sp2) and aliphatic olefinic C(sp2) carbons of two same molecules via dual C–H activation and ortho C–H olefination with various alkenes via distal ester directing group has been developed for the first time.
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4

Zhang, Yanghui, Bo Zhou, and Ailan Lu. "Pd-Catalyzed C–H Silylation Reactions with Disilanes." Synlett 30, no. 06 (2018): 685–93. http://dx.doi.org/10.1055/s-0037-1610339.

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Pd-catalyzed C–H silylation reactions remain underdeveloped. General strategies usually rely on the use of complex bidentate directing groups. C,C-Palladacycles exhibit extremely high reactivity towards hexamethyldisilane and can be disilylated very efficiently. The C,C-palladacycles are prepared through halide-directed C–H activation. This account introduces Pd-catalyzed C–H silylation reactions with di­silanes as the silyl source, and is focused on studies on the silylation of C,C-palladacycles.1 Introduction and Background2 Allylic C–H Silylation Reaction3 Coordinating-Ligand-Directed C–H S
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5

Dutta, Uttam, Sudip Maiti, Trisha Bhattacharya, and Debabrata Maiti. "Arene diversification through distal C(sp2)−H functionalization." Science 372, no. 6543 (2021): eabd5992. http://dx.doi.org/10.1126/science.abd5992.

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Transition metal–catalyzed aryl C−H activation is a powerful synthetic tool as it offers step and atom-economical routes to site-selective functionalization. Compared with proximal ortho-C−H activation, distal (meta- and/or para-) C−H activation remains more challenging due to the inaccessibility of these sites in the formation of energetically favorable organometallic pretransition states. Directing the catalyst toward the distal C−H bonds requires judicious template engineering and catalyst design, as well as prudent choice of ligands. This review aims to summarize the recent elegant discove
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6

Geng, Cuihuan, Sujuan Zhang, Chonggang Duan, Tongxiang Lu, Rongxiu Zhu, and Chengbu Liu. "Theoretical investigation of gold-catalyzed oxidative Csp3–Csp2 bond formation via aromatic C–H activation." RSC Advances 5, no. 97 (2015): 80048–56. http://dx.doi.org/10.1039/c5ra16359e.

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The mechanisms of Selectfluor-mediated homogeneous Au-catalyzed intramolecular C<sub>sp3</sub>–C<sub>sp2</sub> cross-coupling reaction involving direct aryl C<sub>sp2</sub>–H functionalization has been investigated theoretically.
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7

Britton, Luke, Jamie H. Docherty, Andrew P. Dominey, and Stephen P. Thomas. "Iron-Catalysed C(sp2)-H Borylation Enabled by Carboxylate Activation." Molecules 25, no. 4 (2020): 905. http://dx.doi.org/10.3390/molecules25040905.

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Arene C(sp2)-H bond borylation reactions provide rapid and efficient routes to synthetically versatile boronic esters. While iridium catalysts are well established for this reaction, the discovery and development of methods using Earth-abundant alternatives is limited to just a few examples. Applying an in situ catalyst activation method using air-stable and easily handed reagents, the iron-catalysed C(sp2)-H borylation reactions of furans and thiophenes under blue light irradiation have been developed. Key reaction intermediates have been prepared and characterised, and suggest two mechanisti
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8

Dhara, Shubhendu, Raju Singha, Atiur Ahmed та ін. "Synthesis of α, β and γ-carbolines via Pd-mediated Csp2-H/N–H activation". RSC Adv. 4, № 85 (2014): 45163–67. http://dx.doi.org/10.1039/c4ra08457h.

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An efficient method for the synthesis of halo-carbolines has been developed via Pd-catalysed formation of C–N bonds through C<sub>sp2</sub>-H/N–H activation of 4-methyl-N-[2-(pyridine-3-yl)phenyl] benzenesulfonamide derivatives.
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9

Shin, Seohyun, Dongjin Kang, Woo Hyung Jeon, and Phil Ho Lee. "Synthesis of ethoxy dibenzooxaphosphorin oxides through palladium-catalyzed C(sp2)–H activation/C–O formation." Beilstein Journal of Organic Chemistry 10 (May 23, 2014): 1220–27. http://dx.doi.org/10.3762/bjoc.10.120.

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We report an efficient Pd-catalyzed C(sp2)–H activation/C–O bond formation for the synthesis of ethoxy dibenzooxaphosphorin oxides from 2-(aryl)arylphosphonic acid monoethyl esters under aerobic conditions.
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10

Song, Liangliang, Guilong Tian, Johan Van der Eycken, and Erik V. Van der Eycken. "Intramolecular cascade annulation triggered by rhodium(III)-catalyzed sequential C(sp2)–H activation and C(sp3)–H amination." Beilstein Journal of Organic Chemistry 15 (February 27, 2019): 571–76. http://dx.doi.org/10.3762/bjoc.15.52.

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A rhodium(III)-catalyzed intramolecular oxidative annulation of O-substituted N-hydroxyacrylamides for the construction of indolizinones via sequential C(sp2)–H activation and C(sp3)–H amination has been developed. This approach shows excellent functional-group tolerance. The synthesized scaffold forms the core of many natural products with pharmacological relevance.
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11

Sahoo, Sumeet Ranjan, Subhabrata Dutta, Shaeel A. Al-Thabaiti, Mohamed Mokhtar, and Debabrata Maiti. "Transition metal catalyzed C–H bond activation by exo-metallacycle intermediates." Chemical Communications 57, no. 90 (2021): 11885–903. http://dx.doi.org/10.1039/d1cc05042g.

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12

Park, Ji Eun, and Youn K. Kang. "Evidence of a Wheland Intermediate in Carboxylate-Assisted C(sp2)−H Activation by Pd(IV) Active Catalyst Species Studied via DFT Calculations." Catalysts 13, no. 4 (2023): 724. http://dx.doi.org/10.3390/catal13040724.

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Evidence of a Wheland intermediate in carboxylate-assisted C−H activation was found using DFT calculations when the Pd(IV) catalyst species was postulated as the active catalyst species (ACS). In order to delineate the reaction mechanism of Pd-catalyzed bisarylation of 3-alkylbenzofuran, five hypothetical catalyst species, [Pd(OAc)(PMe3)(Ph)] (I), [Pd(OAc)2] (II), [Pd(OAc)2(PMe3)] (III), [Pd(OAc)2(Ph)]+ (IV) and [Pd(OAc)2(PMe3)(Ph)]+ (V) were tested as potential ACS candidates. The catalyst species I, previously reported as an ACS in the context of ambiphilic metal−ligand assistance or a conce
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13

Moghimi, Setareh, Mohammad Mahdavi, Abbas Shafiee, and Alireza Foroumadi. "Transition-Metal-Catalyzed Acyloxylation: Activation of C(sp2)-H and C(sp3)-H Bonds." European Journal of Organic Chemistry 2016, no. 20 (2016): 3282–99. http://dx.doi.org/10.1002/ejoc.201600138.

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14

Prajapati, Ramanand, Ajay Kant Gola, Amrendra Kumar, Shubham Jaiswal, and Narender Tadigoppula. "o-Acetoxylation of oxo-benzoxazines via C–H activation by palladium(ii)/aluminium oxide." New Journal of Chemistry 46, no. 12 (2022): 5719–24. http://dx.doi.org/10.1039/d2nj00134a.

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15

Valentini, Federica, Oriana Piermatti, and Luigi Vaccaro. "Metal and Metal Oxide Nanoparticles Catalyzed C–H Activation for C–O and C–X (X = Halogen, B, P, S, Se) Bond Formation." Catalysts 13, no. 1 (2022): 16. http://dx.doi.org/10.3390/catal13010016.

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The direct functionalization of an inactivated C–H bond has become an attractive approach to evolve toward step-economy, atom-efficient and environmentally sustainable processes. In this regard, the design and preparation of highly active metal nanoparticles as efficient catalysts for C–H bond activation under mild reaction conditions still continue to be investigated. This review focuses on the functionalization of un-activated C(sp3)–H, C(sp2)–H and C(sp)–H bonds exploiting metal and metal oxide nanoparticles C–H activation for C–O and C–X (X = Halogen, B, P, S, Se) bond formation, resulting
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16

Sun, Jinfeng, Fangfeng Chen, Juan Liu, et al. "Reactions of an Anionic Gallylene with Azobenzene or Azide Compounds Through C(sp2)–H and C(sp3)–H Activation." Molecules 29, no. 21 (2024): 5021. http://dx.doi.org/10.3390/molecules29215021.

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The activation of inert C–H bonds remains a challenge in current chemistry. Here, we report the excellent reactivity of the anionic gallylene species [LGa:][Na(THF)3] (L = [(2,6-iPr2C6H3)NC(CH3)]22−, 1) that allows the selective activation one ortho sp2 C–H bond of several azobenzene and azide derivatives at ambient temperature, with the transfer of the hydrogen atom to one of the nitrogen atoms. The process leads to the formation of the aryl amido products [LGa-κ2N,C-PhNN(H)(p-R-C6H3)][Na(solvent)3] (2, R = H solvent = DME (1,2-Dimethoxyethane); 3, R = –OMe, solvent = DME; 4, R = –NMe2 solven
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17

Wang, Xiao, Ming-Zhu Lu, and Teck-Peng Loh. "Transition-Metal-Catalyzed C–C Bond Macrocyclization via Intramolecular C–H Bond Activation." Catalysts 13, no. 2 (2023): 438. http://dx.doi.org/10.3390/catal13020438.

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Macrocycles are commonly synthesized via late-stage macrolactamization and macrolactonization. Strategies involving C–C bond macrocyclization have been reported, and examples include the transition-metal-catalyzed ring-closing metathesis and coupling reactions. In this mini-review, we summarize the recent progress in the direct synthesis of polyketide and polypeptide macrocycles using a transition-metal-catalyzed C–H bond activation strategy. In the first part, rhodium-catalyzed alkene–alkene ring-closing coupling for polyketide synthesis is described. The second part summarizes the synthesis
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18

Zhang, Hongyu, and Shangdong Yang. "Palladium-catalyzed R2(O)P-directed C(sp2)-H activation." Science China Chemistry 58, no. 8 (2015): 1280–85. http://dx.doi.org/10.1007/s11426-015-5382-1.

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19

Sun, Qiao, and Naohiko Yoshikai. "Cobalt-catalyzed C(sp2)–H/C(sp3)–H coupling via directed C–H activation and 1,5-hydrogen atom transfer." Organic Chemistry Frontiers 5, no. 4 (2018): 582–85. http://dx.doi.org/10.1039/c7qo00906b.

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20

Li, Guang-Hui, Dao-Qing Dong, Xian-Yong Yu, and Zu-Li Wang. "Direct synthesis of 8-acylated quinoline N-oxidesviapalladium-catalyzed selective C–H activation and C(sp2)–C(sp2) cleavage." New Journal of Chemistry 43, no. 4 (2019): 1667–70. http://dx.doi.org/10.1039/c8nj05374j.

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An efficient method for the synthesis of 8-acylated quinoline N-oxides from the reaction of quinoline N-oxides with α-diketonesviaC–C bond cleavage was developed. A variety of quinoline N-oxides and α-diketones with different groups was well tolerated in this system.
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21

Bettadapur, Kiran R., Veeranjaneyulu Lanke, and Kandikere Ramaiah Prabhu. "A deciduous directing group approach for the addition of aryl and vinyl nucleophiles to maleimides." Chemical Communications 53, no. 46 (2017): 6251–54. http://dx.doi.org/10.1039/c7cc02392h.

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A Rh(iii)-catalyzed C–H activation followed by conjugate addition to maleimides, using carboxylic acid as a traceless/deciduous directing group, to formally furnish a C<sub>sp2</sub>–C<sub>sp3</sub> bond is presented.
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22

Zucca, Antonio, Sergio Stoccoro, Maria Agostina Cinellu, Giovanni Minghetti, and Mario Manassero. "Cyclometallated derivatives of rhodium(III). Activation of C(sp3)–H vs. C(sp2)–H bonds." Journal of the Chemical Society, Dalton Transactions, no. 19 (1999): 3431–37. http://dx.doi.org/10.1039/a903614h.

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23

Seth, Kapileswar, Manesh Nautiyal, Priyank Purohit, Naisargee Parikh, and Asit K. Chakraborti. "Palladium catalyzed Csp2–H activation for direct aryl hydroxylation: the unprecedented role of 1,4-dioxane as a source of hydroxyl radicals." Chemical Communications 51, no. 1 (2015): 191–94. http://dx.doi.org/10.1039/c4cc06864e.

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24

Uttry, Alexander, and Manuel van Gemmeren. "Direct C(sp3)–H Activation of Carboxylic Acids." Synthesis 52, no. 04 (2019): 479–88. http://dx.doi.org/10.1055/s-0039-1690720.

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Carboxylic acids are important in a variety of research fields and applications. As a result, substantial efforts have been directed towards the C–H functionalization of such compounds. While the use of the carboxylic acid moiety as a native directing group for C(sp2)–H functionalization reactions is well established, as yet there is no general solution for the C(sp3)–H activation of aliphatic carboxylic acids and most endeavors have instead relied on the introduction of stronger directing groups. Recently however, novel ligands, tools, and strategies have emerged, which enable the use of free
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25

Maraswami, Manikantha, and Teck-Peng Loh. "Transition-Metal-Catalyzed Alkenyl sp2 C–H Activation: A Short Account." Synthesis 51, no. 05 (2019): 1049–62. http://dx.doi.org/10.1055/s-0037-1611649.

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Alkenes are ubiquitous in Nature and their functionalization continues to attract attention from the scientific community. On the other hand, activation of alkenyl sp2 C–H bonds is challenging due to their chemical properties. In this short account, we elucidate, discuss and describe the utilization of transition-metal catalysts in alkene activation and provide useful strategies to synthesize organic building blocks in an efficient and sustainable manner.1 Introduction2 Breakthrough3 Controlling E/Z, Z/E Selectivity3.1 Esters and Amides as Directing Groups3.2 The Chelation versus Non-Chelation
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26

Cheng, Huiling, Yubo Jiang, Jianhua Yang, Fen Zhao, Yaowen Liu, and Fang Luo. "Selective Diacetoxylation of Disubstituted 1,2,3-Triazoles through Palladium-Catalyzed C–H Activation." Synlett 29, no. 10 (2018): 1373–78. http://dx.doi.org/10.1055/s-0036-1591564.

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A simple and efficient selective diacetoxylation of 1,4-disubstituted 1,2,3-triazoles by Pd-catalyzed C–H bond activation is described. PhI(OAc)2 was used as an acetyloxy source to convert aromatic sp2 C–H bonds into C–O bonds with high selectivity by employing a 1,2,3-triazole ring as an elegant directing group. A range of 1,2,3-triazoles bearing two acetyloxy groups can be readily synthesized by the reaction.
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27

Liu, Weidong, Qingzhen Yu, Le'an Hu, Zenghua Chen, and Jianhui Huang. "Modular synthesis of dihydro-isoquinolines: palladium-catalyzed sequential C(sp2)–H and C(sp3)–H bond activation." Chemical Science 6, no. 10 (2015): 5768–72. http://dx.doi.org/10.1039/c5sc01482d.

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An efficient synthesis of dihydro-isoquinolines via a Pd–catalyzed double C–H bond activation/annulation featuring a short reaction time, high atom economy and the formation of a sterically less favoured tertiary C–N bond.
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28

Liu, Yunqi, Yudong Yang, Chunxia Wang, Zhishuo Wang, and Jingsong You. "Rhodium(iii)-catalyzed regioselective oxidative annulation of anilines and allylbenzenes via C(sp3)–H/C(sp2)–H bond cleavage." Chemical Communications 55, no. 8 (2019): 1068–71. http://dx.doi.org/10.1039/c8cc09099h.

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As a proof-of-concept, we disclose the rhodium-catalyzed oxidative annulation of anilines with allylbenzenes to afford a variety of indoles, in which the allylic C(sp<sup>3</sup>)–H activation and directed C(sp<sup>2</sup>)–H activation are merged into a single approach for the first time.
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29

Cizikovs, Aleksandrs, and Liene Grigorjeva. "Co(III) Intermediates in Cobalt-Catalyzed, Bidentate Chelation Assisted C(sp2)-H Functionalizations." Inorganics 11, no. 5 (2023): 194. http://dx.doi.org/10.3390/inorganics11050194.

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The C-H bond activation and functionalization is a powerful tool that provides efficient access to various organic molecules. The cobalt-catalyzed oxidative C-H bond activation and functionalization has earned enormous interest over the past two decades. Since then, a wide diversity of synthetic protocols have been published for C-C, C-Het, and C-Hal bond formation reactions. To gain some insights into the reaction mechanism, the authors performed a series of experiments and collected evidence. Several groups have successfully isolated reactive Co(III) intermediates to elucidate the reaction m
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30

Pashazadeh, Rahim, Saideh Rajai-Daryasarei, Siyavash Mirzaei, Mehdi Soheilizad, Samira Ansari, and Meisam Shabanian. "A Regioselective Approach to C3-Aroylcoumarins via Cobalt-Catalyzed­ C(sp2)–H Activation Carbonylation of Coumarins." Synthesis 51, no. 15 (2019): 3014–20. http://dx.doi.org/10.1055/s-0037-1610702.

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A new cobalt-catalyzed C–H bond activation of coumarins with aryl halides or pseudohalides and carbon monoxide insertion to give various 3-aroylcoumarin derivatives is described. It is the first time that CO as C1 feedstock is used as the coupling partners in cobalt-catalyzed regioselective coumarin C–H functionalization reactions. Upon activation with manganese powder, the Co catalyzes the C–H bond activation carbonylation reactions of aryl iodides, bromides, and even triflates under mild conditions, providing the regioselective aroylated products in moderate to good yields.
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31

Verma, Ashish Kumar, Ande Chennaiah, Sateesh Dubbu, and Yashwant D. Vankar. "Palladium catalyzed synthesis of sugar-fused indolines via C(sp2)–H/N H activation." Carbohydrate Research 473 (February 2019): 57–65. http://dx.doi.org/10.1016/j.carres.2018.12.015.

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32

Klare, Hendrik F. T. "Catalytic C–H Arylation of Unactivated C–H Bonds by Silylium Ion-Promoted C(sp2)–F Bond Activation." ACS Catalysis 7, no. 10 (2017): 6999–7002. http://dx.doi.org/10.1021/acscatal.7b02658.

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33

Song, Juan, Yali Li, Wei Sun, et al. "Efficient palladium-catalyzed C(sp2)–H activation towards the synthesis of fluorenes." New Journal of Chemistry 40, no. 11 (2016): 9030–33. http://dx.doi.org/10.1039/c6nj02033j.

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34

Luo, Haiqing, and Xiaolan Li. "Rhodium(III)-Catalyzed C–C Bond Formation by Direct C–H Activation." Synlett, February 18, 2025. https://doi.org/10.1055/s-0043-1775442.

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AbstractTransition-metal-catalyzed functionalizations of C–H bonds to construct C–C bonds represent an ideal route in the synthesis of valuable organic molecules. In particular, rhodium(III)-catalyzed C–H bond activation offers an attractive strategy due to its efficiency and step economy for direct functionalization in organic synthesis. Consequently, recent developments in this area have assured a high level of regioselectivity in C–H functionalization reactions. In this Account, we have summarized our recent achievements in the functionalizations of sp2- and sp3-C–H bonds using rhodium cata
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35

Parmar, Himanshu V., Yash J. Adodariya, Unnati P. Patel, Pranav S. Shrivastav, and Jayesh J. Maru. "Copper‐Catalyzed C(sp2)−C(sp2) Bond Formation via Single C(sp2)−H Activation." ChemistrySelect 9, no. 2 (2024). http://dx.doi.org/10.1002/slct.202303474.

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AbstractThis review provides a comprehensive overview and evaluation of the studies conducted over the past 15 years into copper catalyzed reactions for C(sp2)−C(sp2) bond formation via C(sp2)−H activation. The investigations encompass a wide array of starting materials and substrates. The range of substrates studied has been broadened to encompass C−H activation of aryls, heteroaryls, and alkenyl groups. Furthermore, in some cases only catalytic amounts of copper salts were required to drive the challenging C−H functionalization, indicating a promising avenue for future research.
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36

Tian, Panpan, Chao Feng, and Teck-Peng Loh. "Rhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation." Nature Communications 6, no. 1 (2015). http://dx.doi.org/10.1038/ncomms8472.

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37

Sankar, Rathinam, та Vasuki Gnanasambandam. "Palladium‐Catalyzed 2‐Aminoacetophenone Oxime Directed β‐sp2 and γ‐sp3 C─H Bond Functionalization of Aryl Carboxamides". ChemistrySelect 9, № 45 (2024). http://dx.doi.org/10.1002/slct.202400901.

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AbstractPd(II)‐catalyzed 2‐aminoacetophenone oxime‐assisted sp2 and sp3 C─H arylation of aryl carboxamides is disclosed. The 2‐aminoacetophenone oxime is an N,N‐bidentate auxiliary that proceeds C─H activation through a six‐membered palladacycle intermediate, and the activation/functionalization on C(sp3)─H bond by the six‐membered ligand palladacycle is novel and achieved. This auxiliary facilitates the subsequent sp3 and sp2 C─H bond activation/functionalization in one step. The optimized protocol enables access to various aryl groups at the β‐sp2‐ and γ‐sp3‐centers of aryl carboxamides. The
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38

Hirata, Yuki, Shunsuke Kimura, Kosuke Higashida, Tatsuhiko Yoshino, and Shigeki Matsunaga. "Site‐selective C(sp3)–H and Switchable C(sp3)–H/C(sp2)–H Functionalization Enabled by Electron‐deficient Cp*CF3Ir(III) Catalyst and Photosensitizer." Angewandte Chemie, December 16, 2024. https://doi.org/10.1002/ange.202421026.

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A site‐selective functionalization of a C(sp3)–H bond was achieved in the presence of an intrinsically more reactive C(sp2)–H bond by controlling the orientation of a directing group via a photo‐induced E/Z isomerization of an oxime ether. By combining E/Z isomerization and an electron deficient Cp*CF3Ir(III) catalyst, the scope of oxime ethers in C(sp3)–H functionalization was successfully expanded. Based on this strategy, the order of C–H activation was switchable and successive C(sp3)–H/C(sp2)–H and C(sp2)–H/C(sp3)–H double functionalizations were accomplished to construct densely functiona
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39

Hirata, Yuki, Shunsuke Kimura, Kosuke Higashida, Tatsuhiko Yoshino, and Shigeki Matsunaga. "Site‐selective C(sp3)–H and Switchable C(sp3)–H/C(sp2)–H Functionalization Enabled by Electron‐deficient Cp*CF3Ir(III) Catalyst and Photosensitizer." Angewandte Chemie International Edition, December 16, 2024. https://doi.org/10.1002/anie.202421026.

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A site‐selective functionalization of a C(sp3)–H bond was achieved in the presence of an intrinsically more reactive C(sp2)–H bond by controlling the orientation of a directing group via a photo‐induced E/Z isomerization of an oxime ether. By combining E/Z isomerization and an electron deficient Cp*CF3Ir(III) catalyst, the scope of oxime ethers in C(sp3)–H functionalization was successfully expanded. Based on this strategy, the order of C–H activation was switchable and successive C(sp3)–H/C(sp2)–H and C(sp2)–H/C(sp3)–H double functionalizations were accomplished to construct densely functiona
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40

Panigrahi, Pritishree, Subhendu Ghosh, Tamanna Khandelia, Raju Mandal, and Bhisma K. Patel. "Isoxazole as nitrile synthon: En routes to ortho-alkenylated isoxazole and benzonitrile with allyl sulfone catalyzed by Ru(II)." Chemical Communications, 2023. http://dx.doi.org/10.1039/d3cc02996d.

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Ru (II) catalyzed regioselective Heck-type C-H olefination of isoxazole with unactivated allyl phenyl sulfone is revealed. Solvent DCM offers dual sp2-sp2 C-H activation via N-directed strategy leading to ortho-olefinated isoxazoles...
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41

Ling, Sihao, Qihua Chen, and Zhengkai Chen. "Rh(III)-catalyzed annulation of oxadiazolones with CF3-imidoyl sulfoxonium ylides: access to trifluoromethyl-substituted fused-dihydroisoquinolines." Organic & Biomolecular Chemistry, 2025. https://doi.org/10.1039/d5ob00732a.

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A rhodium(III)-catalyzed redox-neutral C(sp2)–H bond activation and annulation of oxadiazolones and CF3-substituted imidoyl sulfoxonium ylides (TFISYs) has been developed. The cascade C(sp2)–H bond imidoylmethylation and subsequent intramolecular nucleophilic addition sequence...
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42

Wang, Jun, and Mingliang Li. "Recent Advances on Transition-Metal-Catalyzed Asymmetric C–H Arylation Reactions." Synthesis, October 25, 2021. http://dx.doi.org/10.1055/a-1677-5870.

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AbstractTransition-metal-catalyzed asymmetric C–H functionalization has become a powerful strategy to synthesize complex chiral molecules. Recently, catalytic enantioselective C–H arylation has attracted great interest from organic chemists to construct aryl-substituted chiral compounds. In this short review, we highlight recent advances in asymmetric C–H arylation from 2019 to late 2021, including enantioselective C(sp2)–H arylation to construct axial or planar chiral compounds, and enantioselective C(sp3)–H arylation to introduce central chirality via desymmetrization of the methyl group or
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43

"Palladium-Catalyzed Enantioselective meta-C(sp2)–H Activation." Synfacts 14, no. 09 (2018): 0932. http://dx.doi.org/10.1055/s-0037-1610588.

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44

Zhang, Xiang, Rong Zeng, Wan-Cong Liu, Qing-Zhu Li, and Jun-Long Li. "Ultra-Remote Functionalization of Aromatic C–H Bonds via Radical NHC Organocatalysis." Synlett, April 29, 2025. https://doi.org/10.1055/a-2597-0098.

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The selective functionalization of distal C–H bonds, particularly remote aromatic C(sp²)–H bonds, represents a significant challenge in synthetic chemistry. Recently, we have developed an N-heterocyclic carbene (NHC) organocatalytic strategy for the acylation of ultra-remote aryl C(sp2)H bonds located eight bonds away from an activation site. This method proceeds via a novel single-electron pathway, enabling site-selective activation of aryl C–H bonds by in situ generated nitrogen-centered radicals. This approach offers substantial potential for the late-stage functionalization of pharmaceutic
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45

Li, Tiangui, Shiyang Wang, Zongxiang Xia, et al. "Nickel(II)‐Catalyzed Hydrocarbamoylation of Alkynes with Formamides towards Unsaturated Amides." Helvetica Chimica Acta, June 3, 2024. http://dx.doi.org/10.1002/hlca.202400020.

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Ni‐catalyzed activation of C(sp2)‐H bond remains an elusive challenge. Herein, we realized a Ni‐catalyzed selective activation of C(sp2)‐H bond of formamides, which underwent addition reaction with internal alkynes to provide α,β‐unsaturated amide compounds in high yields. The protocol was featured by the cheap and nontoxic catalyst system. Preliminary mechanistic studies shed light on the reaction pathways.
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46

Grigorjeva, Liene, Aleksandrs Cizikovs, Lukass T. Lukasevics, and Paula A. Zagorska. "Cobalt-Catalyzed C–H Bond Functionalization: a Personal Account." Synlett, April 29, 2025. https://doi.org/10.1055/s-0043-1775473.

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AbstractThe development of green and sustainable synthetic methods is of great interest worldwide. Today the direct activation and functionalization of relatively inert C–H bonds is one of the top fields in organic chemistry, and this strategy already represents a sustainable and more environmentally friendly approach due to its atom and step economy compared to alternative C–C and C–Het bond-forming processes. Much progress has been made in developing C–H bond functionalization methods using noble-metal catalysts. Cobalt has recently emerged as an attractive alternative because it is less tox
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47

Lincoln, Zachary, Melissa Hoffbauer, and Vlad Iluc. "Carbon-Carbon Bond Formation by Iron(0)-Olefin Pincer Complex." Synthesis, May 16, 2025. https://doi.org/10.1055/a-2615-1768.

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C-H functionalization is a highly appealing strategy for accessing complex molecular structures. Herein, we show that π-tethered pincer ligands can engage in C-H activation when coordinated to iron. These reactions result in C(sp2)-C(sp2) bond formation through oxidative coupling and β-hydride elimination/reductive elimination pathways with alkynes and isocyanides.
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48

Che, Chi-Ming, Hai-Xu Wang, and Kai Wu. "Metal-Quinoid Carbene Chemistry: From Bonding to C–H Activation Catalysis." Synlett, August 7, 2020. http://dx.doi.org/10.1055/s-0040-1707221.

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This account summarizes our recent work on metal-quinoid carbene (QC) chemistry including (a) dirhodium-catalyzed QC C(sp2)–H insertion reactions enabled by a C-centered carbene-transfer reactivity, (b) the isolation, characterization, and dual reactivity of Ru(II) porphyrin QC complexes, and (c) iridium(III) porphyrin-catalyzed QC C(sp3)–H insertion reaction initiated by an O-centered hydrogen-atom transfer reactivity of metal–QC species.1 Introduction2 Catalytic Quinoid Carbene Insertions into C(sp2)–H Bonds Enabled by Carbene-Transfer Reactivity3 Ruthenium(II) Porphyrin Quinoid Carbene Comp
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Wu, Xin-Xing, Jie Sun, Shaojie Zhang, Ruixue Wang, and Zeng Lv. "Palladium-catalyzed sequential [3+2] cyclization/C-H activation of o-iodostyrenes with cyclopropenones as C2 synthons." Chemical Communications, 2025. https://doi.org/10.1039/d5cc01189b.

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Herein we report a novel palladium-catalyzed synthesis of diverse dihydroindeno[2,1-a]indenes by the reaction of o-iodostyrenes with cyclopropenones. This protocol involves a [3+2] cyclization/C-H activation sequence, forming a C(sp2)-C(sp2) and two...
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Chen, Peng, Zhi-Yong Wang, Jiaxin Wang, Xiao-Shui Peng, and Henry N. C. Wong. "Remote C(sp3)−H Activation: Palladium-Catalyzed Intermolecular Arylation and Alkynylation with Organolithiums and Terminal Alkynes." Organic Chemistry Frontiers, 2022. http://dx.doi.org/10.1039/d2qo00584k.

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1,4-Palladium shift is regarded as one of the solutions towards the challenging remote C(sp3)−H activation. Herein we report two efficient remote C(sp3)−H activation protocols involving palladium-catalyzed C(sp3)−C(sp2) and C(sp3)−C(sp) cross-coupling...
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