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1

Guo, Lirong, Fengting Liu, Liying Wang, et al. "Transition-metal-free aerobic C–O bond formation via C–N bond cleavage." Organic Chemistry Frontiers 7, no. 9 (2020): 1077–81. http://dx.doi.org/10.1039/d0qo00173b.

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We disclosed a TM-free cascade S<sub>N</sub>Ar-[3,3] rearrangement–rearomatization process for the efficient construction of NOBIN-type biaryls from readily available (hetero)arylhydroxylamines and aryltrimethylammonium salts under mild conditions.
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2

Szostak, Michal, and Guangchen Li. "Non-Classical Amide Bond Formation: Transamidation and Amidation of Activated Amides and Esters by Selective N–C/O–C Cleavage." Synthesis 52, no. 18 (2020): 2579–99. http://dx.doi.org/10.1055/s-0040-1707101.

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In the past several years, tremendous advances have been made in non-classical routes for amide bond formation that involve transamidation and amidation reactions of activated amides and esters. These new methods enable the formation of extremely valuable amide bonds via transition-metal-catalyzed, transition-metal-free, or metal-free pathways by exploiting chemoselective acyl C–X (X = N, O) cleavage under mild conditions. In a broadest sense, these reactions overcome the formidable challenge of activating C–N/C–O bonds of amides or esters by rationally tackling nN → π*C=O delocalization in am
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3

Sun, Qiu, Ling He, Jiaxin Cheng, Ze Yang, Yuansheng Li, and Yulan Xi. "Synthesis of Isoxazolines and Isoxazoles via Metal-Free Desulfitative Cyclization." Synthesis 50, no. 12 (2018): 2385–93. http://dx.doi.org/10.1055/s-0037-1609480.

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A novel, one-pot reaction for the synthesis of isoxazolines and isoxazoles is developed via a cascade process under metal-free conditions. The approach involves the formation of intramolecular C–N and C–O bonds and intermolecular C–C bonds from aromatic alkenes or alkynes and N-hydroxysulfonamides using hypervalent iodine(VII) and iodine as the oxidant. Activation of C–H and C–C bonds/construction of C–O bonds/elimination of SO2/C–N bond formation is achieved in sequence­ in the reaction system.
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4

Miyabe, Hideto. "Transition-Metal-Free Activation of Amide Bond by Arynes." Molecules 23, no. 9 (2018): 2145. http://dx.doi.org/10.3390/molecules23092145.

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Highly reactive arynes activate the N–C and C=O bonds of amide groups under transition metal-free conditions. This review highlights the insertion of arynes into the N–C and C=O bonds of the amide group. The insertion of arynes into the N–C bond gives the unstable four-membered ring intermediates, which are easily converted into ortho-disubstituted arenes. On the other hand, the selective insertion of arynes into the C=O bond is observed when the sterically less-hindered formamides are employed to give a reactive transient intermediate. Therefore, the trapping reactions of transient intermedia
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5

Chiummiento, Lucia, Rosarita D’Orsi, Maria Funicello, and Paolo Lupattelli. "Last Decade of Unconventional Methodologies for the Synthesis of Substituted Benzofurans." Molecules 25, no. 10 (2020): 2327. http://dx.doi.org/10.3390/molecules25102327.

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This review describes the progress of the last decade on the synthesis of substituted benzofurans, which are useful scaffolds for the synthesis of numerous natural products and pharmaceuticals. In particular, new intramolecular and intermolecular C–C and/or C–O bond-forming processes, with transition-metal catalysis or metal-free are summarized. (1) Introduction. (2) Ring generation via intramolecular cyclization. (2.1) C7a–O bond formation: (route a). (2.2) O–C2 bond formation: (route b). (2.3) C2–C3 bond formation: (route c). (2.4) C3–C3a bond formation: (route d). (3) Ring generation via in
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6

Kim, Han Byeol, Dong Kyun Han, Jae Kyun Lee, and Seo-Jung Han. "Electrochemical dearomatization of 2-naphthols for C–O bond formation." RSC Advances 15, no. 21 (2025): 16276–80. https://doi.org/10.1039/d5ra02693h.

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7

Li, Shengwang, Guiqin Liu, Zheyan Zhang, et al. "Metal free C–O bond cleavage: a new strategy for the synthesis of substituted oxazoles." RSC Advances 14, no. 38 (2024): 28210–14. http://dx.doi.org/10.1039/d4ra05122j.

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A strategy for C–O bond cleavage of ester for the synthesis of substituted oxazoles was developed. The synthesis proceeded smoothly under metal-free conditions, combining C–O bond cleavage, C–N and C–O bond formation in one pot.
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8

Luo, Shuang, Ziwei Hu, and Qiang Zhu. "Dearomative C–C and C–N bond cleavage of 2-arylindoles: transition-metal-free access to 2-aminoarylphenones." Organic Chemistry Frontiers 3, no. 3 (2016): 364–67. http://dx.doi.org/10.1039/c5qo00394f.

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A transition-metal-free conversion of 2-arylindoles to 2-aminoarylphenones, using environmentally benign O<sub>2</sub> as the sole oxidant, has been developed. This novel oxidative dearomatization process involves cleavage of two C–C and one C–N bonds followed by new C–C and C–O bond formation.
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9

Shi, Yijun, Xuejing Liu, Han Cao, et al. "Conversion of esters to thioesters under mild conditions." Organic & Biomolecular Chemistry 19, no. 13 (2021): 2991–96. http://dx.doi.org/10.1039/d1ob00187f.

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10

Narayan, Rishikesh, Kiran Matcha, and Andrey P. Antonchick. "Metal-Free Oxidative CC Bond Formation through CH Bond Functionalization." Chemistry - A European Journal 21, no. 42 (2015): 14678–93. http://dx.doi.org/10.1002/chem.201502005.

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11

Meng, Ge, Pengfei Li, Kai Chen, and Linghua Wang. "Recent Advances in Transition-Metal-Free Aryl C–B Bond Formation." Synthesis 49, no. 21 (2017): 4719–30. http://dx.doi.org/10.1055/s-0036-1590913.

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Arylboronic acids and their derivatives are widely used in organic synthesis. Conventional methods for their preparation require either reactive organometallic reagents or transition-metal-mediated processes. In recent years, transition-metal-free reactions for aryl C–B bond formation that obviate preformed organometallic reagents have gained interest and have developed rapidly. These new reactions have shown significant advantages for the preparation of functionalized molecules. In this review, an overview of the recent advances in transition-metal-free aromatic borylation reactions is provid
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12

Saidalimu, Ibrayim, Shugo Suzuki, Etsuko Tokunaga, and Norio Shibata. "Successive C–C bond cleavage, fluorination, trifluoromethylthio- and pentafluorophenylthiolation under metal-free conditions to provide compounds with dual fluoro-functionalization." Chemical Science 7, no. 3 (2016): 2106–10. http://dx.doi.org/10.1039/c5sc04208a.

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13

Suresh, Kumar Sythana, and R. Bhagat Pundlik. "Metal free C-O bond formation in electron deficient aromatic compounds mediated by tetrabutylammonium hydroxide : Application to nimesulide and paracetamol." Journal of Indian Chemical Society Vol. 92, Apr 2015 (2015): 563–65. https://doi.org/10.5281/zenodo.5596290.

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Pharmaceutical Development, AstraZeneca India Pvt. Ltd., Bellary Road, Bangalore-560 024, India Chemistry Division, School of Advanced Sciences, VIT University, Vellore-632 014, Tamilnadu, India <em>E-mail </em>: drprbhagat111@gmail.com A mild and efficient method for carbon-oxygen bond formation for the synthesis of aryl ethers has been demonstrated using stoichiometric amount of alcohol and tetrabutylammonium hydroxide (TBAH). The protocol is free from the metal alkoxides, inorganic bases or metal catalysts. This methodology has been applied for synthesis of paracetamol and nimesulide interm
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14

Guo, Li-Na, Zhi-Qiang Deng, Yong Wu, and Jie Hu. "Transition-metal free alkylarylation of acrylamides initiated by radical C–C bond cleavage of the tertiary cycloalkanols." RSC Advances 6, no. 32 (2016): 27000–27003. http://dx.doi.org/10.1039/c6ra03431d.

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An efficient Na<sub>2</sub>S<sub>2</sub>O<sub>8</sub>-promoted radical cyclization reaction of acrylamides with the tertiary cycloalkanols has been developed. This one pot procedure involves a tandem C–C bond cleavage and two C–C bonds formation process.
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15

Zhang, Jing-Wen, Wan-Wan Yang, Lu-Lu Chen, Pei Chen, Yan-Bo Wang, and Dan-Yun Chen. "An efficient tandem synthesis of chromones from o-bromoaryl ynones and benzaldehyde oxime." Organic & Biomolecular Chemistry 17, no. 32 (2019): 7461–67. http://dx.doi.org/10.1039/c9ob01387c.

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16

Yi, Xiangyan, Jiajun Feng, Fei Huang, and Jonathan Bayldon Baell. "Metal-free C–C, C–O, C–S and C–N bond formation enabled by SBA-15 supported TFMSA." Chemical Communications 56, no. 8 (2020): 1243–46. http://dx.doi.org/10.1039/c9cc08389h.

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The intermolecular C–C, C–O, C–S and C–N bonds construction between diazo compounds and acyclic, cyclic 1,3-dicarbonyl compounds, thiophenol, alkynes were developed by using a TFMSA@SBA-15, providing a metal-free and eco-friendly platform.
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17

Chen, Xiuling, Yan Li, Minghu Wu, et al. "An efficient method for the preparation of tert-butyl esters from benzyl cyanide and tert-butyl hydroperoxide under the metal free condition." RSC Advances 6, no. 104 (2016): 102023–27. http://dx.doi.org/10.1039/c6ra20966a.

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A novel protocol to synthesize tert-butyl esters from benzyl cyanides and tert-butyl hydroperoxide has been successfully achieved. Csp<sup>3</sup>–H bond oxidation, C–CN bond cleavage and C–O bond formation proceeded smoothly in one pot under the metal-free condition.
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18

Yang, Xue-Yan, Ruizhe Wang, Lu Wang та ін. "K2S2O8-promoted C–Se bond formation to construct α-phenylseleno carbonyl compounds and α,β-unsaturated carbonyl compounds". RSC Advances 10, № 48 (2020): 28902–5. http://dx.doi.org/10.1039/d0ra05927g.

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K<sub>2</sub>S<sub>2</sub>O<sub>8</sub>-promoted C–Se bond formation from the cross-coupling of C(sp<sup>3</sup>)–H bond adjacent to carbonyl group with diphenyl diselenide under metal-free conditions.
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19

Luo, Tian, Shanghui Tian, Jie-Ping Wan, and Yunyun Liu. "Recent Advances in Transition Metal-Free Halogenation of C(sp2)-H Bonds." Current Organic Chemistry 25, no. 10 (2021): 1180–93. http://dx.doi.org/10.2174/1385272825666210122094423.

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C-X (X = halogen) bonds are indispensable functional groups in organic synthesis by mediating a massive number of important organic reactions. While a variety of different catalytic strategies are available for generating C-X bonds, those methods enabling the C-X bond formation under transition metal-free conditions via the C-H bond functionalization are particularly interesting because of the inherent atom economy and environmental friendliness associated with such methods. Herein, the advancements in the transition metal-free halogenation of C(2)-H bond are reviewed.
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20

Raji Reddy, Chada, and Motatipally Damoder Reddy. "A Metal-Free Tandem C–C/C–O Bond Formation Approach to Diversely Functionalized Tetrasubstituted Furans." Journal of Organic Chemistry 79, no. 1 (2013): 106–16. http://dx.doi.org/10.1021/jo4023342.

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21

Peng, Jinsong, Cuijuan Zong, Min Ye, et al. "Direct transition-metal-free intramolecular C–O bond formation: synthesis of benzoxazole derivatives." Org. Biomol. Chem. 9, no. 4 (2011): 1225–30. http://dx.doi.org/10.1039/c0ob00454e.

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22

Adib, Mehdi, Rahim Pashazadeh, Seyed Gohari, and Fatemeh Shahsavari. "Metal-Free Oxidative C=C Bond Cleavage of Electron-Deficient Enamines Promoted by tert-Butyl Hydroperoxide." Synlett 28, no. 12 (2017): 1481–85. http://dx.doi.org/10.1055/s-0036-1588990.

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A novel tert-butyl hydroperoxide (TBHP)-promoted oxidative C=C double-bond cleavage of enamines is described. Heating a solution of an electron-deficient enamine in chlorobenzene at 80 °C in the presence of TBHP for two hours led to cleavage of the C=C bond. This study offers a new strategy to carry out C=O double-bond formation by the use of TBHP.
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23

Ek, Fredrik, Oskar Axelsson, Lars-Göran Wistrand, and Torbjörn Frejd. "Aromatic Allylation via Diazotization: Metal-Free C−C Bond Formation." Journal of Organic Chemistry 67, no. 18 (2002): 6376–81. http://dx.doi.org/10.1021/jo0258103.

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24

Tian, Jingxin, Shanshan Yuan, Fuhong Xiao, Huawen Huang, and Guo-Jun Deng. "Concise synthesis of N-thiomethyl benzoimidazoles through base-promoted sequential multicomponent assembly." RSC Advances 9, no. 52 (2019): 30570–74. http://dx.doi.org/10.1039/c9ra06144d.

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25

Venkateswarlu, Vunnam, K. A. Aravinda Kumar, Sorav Gupta, Deepika Singh, Ram A. Vishwakarma та Sanghapal D. Sawant. "DMSO/I2 mediated C–C bond cleavage of α-ketoaldehydes followed by C–O bond formation: a metal-free approach for one-pot esterification". Organic & Biomolecular Chemistry 13, № 29 (2015): 7973–78. http://dx.doi.org/10.1039/c5ob01015b.

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26

Liu, Zijian, Kunbing Ouyang, and Nianfa Yang. "The thiolation of pentafluorobenzene with disulfides by C–H, C–F bond activation and C–S bond formation." Organic & Biomolecular Chemistry 16, no. 6 (2018): 988–92. http://dx.doi.org/10.1039/c7ob02836a.

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27

Narayan, Rishikesh, Kiran Matcha, and Andrey P. Antonchick. "ChemInform Abstract: Metal-Free Oxidative C-C Bond Formation Through C-H Bond Functionalization." ChemInform 46, no. 50 (2015): no. http://dx.doi.org/10.1002/chin.201550213.

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28

Fang, Xiang, Xueyan Yang, Tongle Shao, Jun Zhou, Chen Jin та Fanhong Wu. "I2/TBHP-Promoted Approach to α-Keto Esters from Trifluoromethyl β-Diketones and Alcohols via C–C Bond Cleavage". Synlett 28, № 15 (2017): 2018–23. http://dx.doi.org/10.1055/s-0036-1588833.

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A metal-free oxidative coupling reaction of trifluoromethyl β-diketones with alcohols for the synthesis of α-keto esters in good to excellent yields has been developed. Preliminary mechanistic studies suggest that an I2/TBHP promoted sequential iodination, C–C bond cleavage, C–O bond formation and oxidation pathway is involved in this reaction.
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29

Deshidi, Ramesh, Shekaraiah Devari, and Bhahwal Ali Shah. "Metal free access to quinolines via C–C bond cleavage of styrenes." Organic Chemistry Frontiers 2, no. 5 (2015): 515–19. http://dx.doi.org/10.1039/c5qo00010f.

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A new metal free self-sorting tandem reaction between styrenes and anilines to access 2,4-disubstituted quinolines, involving simultaneous C–C and C–N bond formation along with a C–C bond cleavage, has been developed.
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30

Zhao, Xiuli, Mengmeng Huang, Yabo Li, Jianye Zhang, Jung Keun Kim, and Yangjie Wu. "Stepwise photosensitized C(sp3)–C(CO) bond cleavage and C–P bond formation of 1,3-dicarbonyls with arylphosphine oxides." Organic Chemistry Frontiers 6, no. 9 (2019): 1433–37. http://dx.doi.org/10.1039/c9qo00075e.

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31

Qiu, Jun, and Ronghua Zhang. "Transition-metal-free oxidative carboazidation of acrylamides via cascade C–N and C–C bond-forming reactions." Org. Biomol. Chem. 12, no. 25 (2014): 4329–34. http://dx.doi.org/10.1039/c4ob00720d.

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A novel transition-metal-free oxidative carboazidation of acrylamides using inexpensive NaN<sub>3</sub> and K<sub>2</sub>S<sub>2</sub>O<sub>8</sub> was achieved, which not only provided an efficient method to prepare various N<sub>3</sub>-substituted oxindoles, but also represented a novel strategy for C–N and C–C bond formation via a free-radical cascade process.
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32

Yang, Xifa, Guolin Cheng, Jinhai Shen, Changsheng Kuai, and Xiuling Cui. "Cleavage of the C–C triple bond of ketoalkynes: synthesis of 4(3H)-quinazolinones." Organic Chemistry Frontiers 2, no. 4 (2015): 366–68. http://dx.doi.org/10.1039/c4qo00260a.

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33

Sharma, Shubham, Dharmender Singh, Sunit Kumar, et al. "An efficient metal-free and catalyst-free C–S/C–O bond-formation strategy: synthesis of pyrazole-conjugated thioamides and amides." Beilstein Journal of Organic Chemistry 19 (March 2, 2023): 231–44. http://dx.doi.org/10.3762/bjoc.19.22.

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An operationally simple and metal-free approach is described for the synthesis of pyrazole-tethered thioamide and amide conjugates. The thioamides were generated by employing a three-component reaction of diverse pyrazole C-3/4/5 carbaldehydes, secondary amines, and elemental sulfur in a single synthetic operation. The advantages of this developed protocol refer to the broad substrate scope, metal-free and easy to perform reaction conditions. Moreover, the pyrazole C-3/5-linked amide conjugates were also synthesized via an oxidative amination of pyrazole carbaldehydes and 2-aminopyridines usin
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34

Zhang, Honglin, Changduo Pan, Ning Jin, Zhangxi Gu, Hongwen Hu, and Chengjian Zhu. "Metal-free cascade construction of C–C bonds by activation of inert C(sp3)–H bonds." Chemical Communications 51, no. 7 (2015): 1320–22. http://dx.doi.org/10.1039/c4cc08629e.

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35

Uygur, Mustafa, Tobias Danelzik, and Olga García Mancheño. "Metal-free desilylative C–C bond formation by visible-light photoredox catalysis." Chemical Communications 55, no. 20 (2019): 2980–83. http://dx.doi.org/10.1039/c8cc10239b.

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36

Zhao, Jian-Nan, Muzaffar Kayumov, Dong-Yu Wang, and Ao Zhang. "Transition-Metal-Free Aryl–Heteroatom Bond Formation via C–S Bond Cleavage." Organic Letters 21, no. 18 (2019): 7303–6. http://dx.doi.org/10.1021/acs.orglett.9b02584.

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37

Samanta, Rajarshi, Kiran Matcha, and Andrey P. Antonchick. "Metal-Free Oxidative Carbon-Heteroatom Bond Formation Through C-H Bond Functionalization." European Journal of Organic Chemistry 2013, no. 26 (2013): 5769–804. http://dx.doi.org/10.1002/ejoc.201300286.

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38

Raji Reddy, Chada, and Motatipally Damoder Reddy. "ChemInform Abstract: A Metal-Free Tandem C-C/C-O Bond Formation Approach to Diversely Functionalized Tetrasubstituted Furans." ChemInform 45, no. 21 (2014): no. http://dx.doi.org/10.1002/chin.201421116.

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39

Liang, Zhi-Peng, Ying-Xin Yu, Yang Wang, Zheng-Guang Wu, and Yuan-Yuan Sun. "Oxidative Annulation of Diphenylpropanamides via In Situ Hypervalent Iodine-Promoted Intramolecular C–N/C–O Bond Formation." SynOpen 05, no. 04 (2021): 327–34. http://dx.doi.org/10.1055/s-0040-1719861.

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AbstractAn aryl iodide catalyzed intramolecular oxidative transformation of diphenylpropanamide derivatives is described that can readily afford the C–N/C–O coupling products in a single step. The speed of the 1,3-aryl iodide migration process determines the diversity of target compound generation in this reaction. This straightforward approach can be performed with the use of inexpensive and readily available catalyst, transition-metal-free, mild conditions and good functional group tolerance.
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40

Dong, Dao-Qing, Shuang-Hong Hao, Dao-Shan Yang, Li-Xia Li, and Zu-Li Wang. "Sulfenylation of C-H Bonds for C-S Bond Formation under Metal-Free Conditions." European Journal of Organic Chemistry 2017, no. 45 (2017): 6576–92. http://dx.doi.org/10.1002/ejoc.201700853.

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41

Yang, Daoshan, Kelu Yan, Wei Wei, et al. "Metal-free n-Et4NBr-catalyzed radical cyclization of disulfides and alkynes leading to benzothiophenes under mild conditions." RSC Adv. 4, no. 89 (2014): 48547–53. http://dx.doi.org/10.1039/c4ra08260e.

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The title reaction involves metal free TEAB-catalyzed S–S bond cleavage, C–S bond formation and C–C bond formation; it uses readily available disulfides and alkynes as substrates, and environmentally friendly TEAB as catalyst to synthesize useful benzothiophene derivatives.
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42

Feng, Enguang, He Huang, Yu Zhou, Deju Ye, Hualiang Jiang, and Hong Liu. "Metal-Free Synthesis of 2-Substituted (N, O, C) Benzothiazoles via an Intramolecular C−S Bond Formation." Journal of Combinatorial Chemistry 12, no. 4 (2010): 422–29. http://dx.doi.org/10.1021/cc9001839.

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43

Li, Qiyang, Haiyan Zhang, and Wenbo Liu. "Research Progress in Transition-Metal-Free C—Si Bond Formation." Chinese Journal of Organic Chemistry 43, no. 10 (2023): 3470. http://dx.doi.org/10.6023/cjoc202307017.

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44

Cai, Shujun, Zheming Xiao, Jinjie Ou, Yingbo Shi, and Shuanhu Gao. "A photo-induced C–C bond formation methodology to construct tetrahydrofluorenones and their related structures." Organic Chemistry Frontiers 3, no. 3 (2016): 354–58. http://dx.doi.org/10.1039/c5qo00392j.

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45

Xie, Hao, Guozheng Li, Feng Zhang, Fuhong Xiao, and Guo-Jun Deng. "Efficient synthesis of 1,2-benzisothiazoles from o-haloarylamidines and elemental sulfur via N–S/C–S bond formation under transition-metal-free conditions." Green Chemistry 20, no. 4 (2018): 827–31. http://dx.doi.org/10.1039/c7gc03599c.

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Facile synthesis of 1,2-benzisothiazoles from amidines and elemental sulfur via N–S/C–S bond formation under transition-metal-free conditions has been developed with good tolerance of a broad range of functional groups.
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46

Peng, Jinsong, Cuijuan Zong, Min Ye, et al. "ChemInform Abstract: Direct Transition-Metal-Free Intramolecular C-O Bond Formation: Synthesis of Benzoxazole Derivatives." ChemInform 42, no. 23 (2011): no. http://dx.doi.org/10.1002/chin.201123116.

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47

Livingstone, Keith, Sophie Bertrand, Jenna Mowat, and Craig Jamieson. "Metal-free C–C bond formation via coupling of nitrile imines and boronic acids." Chemical Science 10, no. 44 (2019): 10412–16. http://dx.doi.org/10.1039/c9sc03032h.

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48

Yan, Rulong, Xiaoni Li, Xiaodong Yang, Xing Kang, Likui Xiang, and Guosheng Huang. "A novel one-pot method for the synthesis of substituted furopyridines: iodine-mediated oxidation of enaminones by tandem metal-free cyclization." Chemical Communications 51, no. 13 (2015): 2573–76. http://dx.doi.org/10.1039/c4cc08834d.

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A novel iodine-mediated oxidative tandem cyclization reaction of simple enaminones has been developed for the synthesis of substituted furopyridines through C–C/C–N/C–O bond formation in a one-pot procedure.
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49

Fan, Wei, Kwong-Yuen Chen, Qi-Peng Chen, Guigen Li, and Bo Jiang. "Facile synthesis of benzo[b]thiophenes via metal-free radical-triggered intramolecular C–S bond formation." Organic & Biomolecular Chemistry 15, no. 31 (2017): 6493–99. http://dx.doi.org/10.1039/c7ob01515a.

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A facile method for the synthesis of benzo[b]thiophenes with good to excellent yields via metal-free intramolecular C–S bond formation has been developed by utilizing I<sub>2</sub> as a catalyst and O<sub>2</sub> from air as an oxidant (20 examples).
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50

Li, Ping-Gui, Cheng Yan, Shuai Zhu, Shu-Hui Liu, and Liang-Hua Zou. "Direct construction of benzimidazo[l,2-c]quinazolin-6-ones via metal-free oxidative C–C bond cleavage." Organic Chemistry Frontiers 5, no. 23 (2018): 3464–68. http://dx.doi.org/10.1039/c8qo01039k.

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