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Regioselectivity in the Iridium-Catalyzed [2 + 2 + 2] Cycloaddition of Unsymmetrical α,ω-Diynes with Nitrile: A DFT Study

Cite this: Organometallics 2020, 39, 11, 2091–2101
Publication Date (Web):May 28, 2020
https://doi.org/10.1021/acs.organomet.0c00152
Copyright © 2020 American Chemical Society

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    Abstract

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    The high regioselectivity of the iridium-catalyzed [2 + 2 + 2] cycloaddition of unsymmetrical α,ω-diynes with nitriles was experimentally determined by Takeuchi and co-workers. In the present study, the regioselectivity in the iridium-catalyzed [2 + 2 + 2] cycloadditions of phenyl- and trimethylsilyl-substituted α,ω-diynes with acetonitrile was examined using PBE-D2-level DFT calculations. The obtained results show that the pathways that produce the pyridine substituted with a phenyl group at the α-position are preferred in the case of a phenyl-substituted diyne, while the pathways that yield the pyridine substituted with a trimethylsilyl group at the β-position are favored in the reaction of a trimethylsilyl-substituted diyne. The obtained results agree with experimentally observed regioselectivities. The structural configuration around the iridium atom affects the energetically preferred pathway beyond the formation of the end-on complex between acetonitrile and iridacyclopentadiene. In addition, both the steric and electronic effects of the substituents on the α-carbon atom play important roles in determining the regioselectivity.

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    Tables listing . . The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.organomet.0c00152.

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    Cited By

    This article is cited by 7 publications.

    1. Jordan L. Harper, Stephanie Felten, Ryan M. Stolley, Alexander S. Hegg, Paul H.-Y. Cheong, Janis Louie. Origins of Regio- and Chemoselectivity in Iron-PDAI-Catalyzed [2+2+2] Cycloaddition Syntheses of 4,6-Disubstituted 2-Aminopyridines. ACS Catalysis 2021, 11 (23) , 14677-14687. https://doi.org/10.1021/acscatal.1c03871
    2. Il Young Cho, Woo Gyum Kim, Ji Hwan Jeon, Jeong Woo Lee, Jeong Kon Seo, Jongcheol Seo, Sung You Hong. Nickelocene as an Air- and Moisture-Tolerant Precatalyst in the Regioselective Synthesis of Multisubstituted Pyridines. The Journal of Organic Chemistry 2021, 86 (14) , 9328-9343. https://doi.org/10.1021/acs.joc.1c00577
    3. Hao Wang, Bolin Qiao, Jide Zhu, Huosheng Guo, Zhen Zhang, Kai Yang, Shi-Jun Li, Yu Lan, Qiuling Song. Enantio- and regioselective [2 + 2 + 2] cycloaddition of BN-diynes for construction of C-B axial chirality. Chem 2023, 22 https://doi.org/10.1016/j.chempr.2023.09.017
    4. Xin-Rui Zhu, De-Cai Fang. DFT study on stereoselective Rh-catalyzed intramolecular [2 + 2 + 2] cycloaddition of allene–ene–ynes. Organic Chemistry Frontiers 2023, 10 (11) , 2624-2634. https://doi.org/10.1039/D3QO00363A
    5. Takahiro Sawano, Kaho Takamura, Tomoka Yoshikawa, Kayo Murata, Marina Koga, Risa Yamada, Takahide Saito, Kazumasa Tabata, Yugo Ishii, Wataru Kashihara, Tatsuya Nishihara, Kazuhito Tanabe, Tadashi Suzuki, Ryo Takeuchi. Synthesis of azafluoranthenes by iridium-catalyzed [2 + 2 + 2] cycloaddition and evaluation of their fluorescence properties. Organic & Biomolecular Chemistry 2023, 21 (2) , 323-331. https://doi.org/10.1039/D2OB01921C
    6. Anders Brakestad, Peter Wind, Stig Rune Jensen, Luca Frediani, Kathrin Helen Hopmann. Multiwavelets applied to metal–ligand interactions: Energies free from basis set errors. The Journal of Chemical Physics 2021, 154 (21) https://doi.org/10.1063/5.0046023
    7. Tatsuki Nagata, Yasushi Obora. Transition‐Metal‐Mediated/Catalyzed Synthesis of Pyridines, Pyrimidines, and Triazines by [2+2+2] Cycloaddition Reactions. Asian Journal of Organic Chemistry 2020, 9 (10) , 1532-1547. https://doi.org/10.1002/ajoc.202000240

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