One-Step Annulative π-Extension of Alkynes with Dibenzosiloles or Dibenzogermoles by Palladium/o-chloranil Catalysis
Dr. Kyohei Ozaki
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorKeiichiro Murai
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorWataru Matsuoka
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorDr. Katsuaki Kawasumi
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorCorresponding Author
Dr. Hideto Ito
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Kenichiro Itami
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya, 464-8601 Japan
JST-ERATO, Itami Molecular Nanocarbon Project, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorDr. Kyohei Ozaki
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorKeiichiro Murai
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorWataru Matsuoka
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorDr. Katsuaki Kawasumi
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorCorresponding Author
Dr. Hideto Ito
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Kenichiro Itami
Graduate School of Science, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya, 464-8601 Japan
JST-ERATO, Itami Molecular Nanocarbon Project, Nagoya University, Chikusa, Nagoya, 464-8602 Japan
Search for more papers by this authorAbstract
Reliable and short synthetic routes to polycyclic aromatic hydrocarbons and nanographenes are important in materials science. Herein, we report an efficient one-step annulative π-extension reaction of alkynes that provides access to diarylphenanthrenes and related nanographene precursors. In the presence of a cationic palladium/o-chloranil catalyst system and dibenzosiloles or dibenzogermoles as π-extending agents, a variety of diarylacetylenes are transformed successfully into 9,10-diarylphenanthrenes in a single step with good functional-group tolerance. Furthermore, double π-extension reactions of 1,4-bis(phenylethynyl)benzene and diphenyl-1,3-butadiyne are demonstrated, affording oligoarylene products, which show potential for application in the synthesis of larger polycyclic aromatic hydrocarbons and nanographenes.
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References
- 1
- 1aV. Georgakilas, J. A. Perman, J. Tucek, R. Zboril, Chem. Rev. 2015, 115, 4744;
- 1bK. Itami, Pure Appl. Chem. 2012, 84, 907;
- 1cJ. Wu, W. Pisula, K. Müllen, Chem. Rev. 2007, 107, 718;
- 1dM. D. Watson, A. Fechtenkötter, K. Müllen, Chem. Rev. 2001, 101, 1267;
- 1eY. Segawa, H. Ito, K. Itami, Nat. Rev. Mater. 2016, 1, 15002.
- 2
- 2aR. Rieger, K. Müllen, J. Phys. Org. Chem. 2010, 23, 315;
- 2bZ. Sun, Q. Ye, C. Chi, J. Wu, Chem. Soc. Rev. 2012, 41, 7857;
- 2cS. Dutta, K. Wakabayashi, Sci. Rep. 2012, 2, 519;
- 2dK. Ritter, J. W. Lyding, Nat. Mater. 2009, 8, 235.
- 3Selected reviews:
- 3aM. Grzybowski, K. Skonieczny, H. Butenschön, D. T. Gryko, Angew. Chem. Int. Ed. 2013, 52, 9900; Angew. Chem. 2013, 125, 10084;
- 3bL. Chen, Y. Hernandez, X. Feng, K. Müllen, Angew. Chem. Int. Ed. 2012, 51, 7640; Angew. Chem. 2012, 124, 7758;
- 3cX. Feng, W. Pisula, K. Müllen, Pure Appl. Chem. 2009, 81, 2203.
- 4
- 4aA. Narita, X. Feng, Y. Hernandez, S. A. Jensen, M. Bonn, H. Yang, I. A. Verzhbitskiy, C. Casiraghi, M. R. Hansen, A. H. R. Koch, G. Fytas, O. Ivasenko, B. Li, K. S. Mali, T. Balandina, S. Mahesh, S. D. Feyter, K. Müllen, Nat. Chem. 2014, 6, 126;
- 4bM. G. Schwab, A. Narita, Y. Hernandez, T. Balandina, K. S. Mali, S. D. Feyter, X. Feng, K. Müllen, J. Am. Chem. Soc. 2012, 134, 18169;
- 4cY. Fogel, L. Zhi, A. Rouhanipour, D. Andrienko, H. J. Räder, K. Müllen, Macromolecules 2009, 42, 6878;
- 4dJ. Wu, L. Gherghel, M. D. Watson, J. Li, Z. Wang, C. D. Simpson, U. Kolb, K. Müllen, Macromolecules 2003, 36, 7082.
- 5Selected recent examples:
- 5aK. Y. Cheung, X. Xu, Q. Miao, J. Am. Chem. Soc. 2015, 137, 3910;
- 5bH.-F. Lee, P.-H. Wang, Y.-C. Huang, W.-H. Su, R. Gopal, C. C. Lee, S. Holdcroft, W.-Y. Huang, J. Polym. Sci. Part A 2014, 52, 2579;
- 5cC. M. Thompson, G. T. McCandless, S. N. Wijenayake, O. Alfarawati, M. Jahangiri, A. Kokash, Z. Tran, R. A. Smaldone, Macromolecules 2014, 47, 8645;
- 5dT. Yu, D. P.-K. Tsang, V. K.-M. Au, W. H. Lam, M.-Y. Chan, V. W.-W. Yam, Chem. Eur. J. 2013, 19, 13418;
- 5eR. Hu, J. W. Y. Lam, Y. Liu, X. Zhang, B. Z. Tang, Chem. Eur. J. 2013, 19, 5617.
- 6S. Suzuki, Y. Segawa, K. Itami, J. Yamaguchi, Nat. Chem. 2015, 7, 227.
- 7
- 7aN. Asao, T. Nogami, S. Lee, Y. Yamamoto, J. Am. Chem. Soc. 2003, 125, 10921; Selected recent examples:
- 7bB. Guo, Y. Zhou, L. Zhang, R. Hua, J. Org. Chem. 2015, 80, 7635;
- 7cH. Arslan, K. L. Walker, W. R. Dichtel, Org. Lett. 2014, 16, 5926;
- 7dS. Hein, H. Arslan, I. Keresztes, W. R. Dichtel, Org. Lett. 2014, 16, 4416;
- 7eZ. He, X. Xu, X. Zheng, T. Ming, Q. Miao, Chem. Sci. 2013, 4, 4525;
- 7fH. Arslan, J. D. Saathoff, D. N. Bunck, P. Clancy, W. D. Dichtel, Angew. Chem. Int. Ed. 2012, 51, 12051; Angew. Chem. 2012, 124, 12217;
- 7gK. S. Prakash, R. Nagarajan, Adv. Synth. Catal. 2012, 354, 1566;
- 7hX.-L. Fang, R.-Y. Tang, X.-G. Zhang, P. Zhong, C.-L. Deng, J.-H. Li, J. Organomet. Chem. 2011, 696, 352.
- 8
- 8aK. Ozaki, K. Kawasumi, M. Shibata, H. Ito, K. Itami, Nat. Commun. 2015, 6, 6251;
- 8bY. Yano, H. Ito, Y. Segawa, K. Itami, Synlett 2016, 27, 2081;
- 8cK. Kato, Y. Segawa, K. Itami, Can. J. Chem. 2016, just-in article. DOI: 10.1139/cjc-2016-0467.
- 9
- 9aQ. Chen, J. Zhao, Y. Ishikawa, N. Asao, Y. Yamamoto, T. Jin, Org. Lett. 2013, 15, 5766;
- 9bF. Jafarpour, H. Hazrati, S. Nouraldinmousa, Org. Lett. 2013, 15, 3816;
- 9cA. Matsumoto, L. Ilies, E. Nakamura, J. Am. Chem. Soc. 2011, 133, 6557;
- 9dT. Fukutani, K. Hirano, T. Satoh, M. Miura, J. Org. Chem. 2011, 76, 2867;
- 9eC. Wang, S. Rakshit, F. Glorius, J. Am. Chem. Soc. 2010, 132, 14006;
- 9fA. A. Cant, L. Roberts, M. F. Greaney, Chem. Commun. 2010, 46, 8671;
- 9gT. Schaub, M. Backes, U. Radius, Organometallics 2006, 25, 4196;
- 9hT. Schaub, U. Radius, Chem. Eur. J. 2005, 11, 5024;
- 9iC. Müller, R. J. Lachicotte, W. Jones, Organometallics 2002, 21, 1975;
- 9jC. N. Iverson, W. D. Jones, Organometallics 2001, 20, 5745;
- 9kD. Peña, D. Pérez, E. Guitián, L. Castedo, J. Am. Chem. Soc. 1999, 121, 5827;
- 9lR. Larock, M. J. Doty, Q. Tian, J. M. Zenner, J. Org. Chem. 1997, 62, 7536;
- 9mG. Dyker, A. Kellner, Tetrahedron Lett. 1994, 35, 7633;
- 9nT. Nagata, K. Hirano, T. Satoh, M. Miura, J. Org. Chem. 2014, 79, 8960;
- 9oT. Nagata, T. Satoh, Y. Nishii, M. Miura, Synlett 2016, 11, 1707;
- 9pY. Shoji, N. Tanaka, S. Muranaka, N. Shigeno, H. Sugiyama, K. Takenouchi, F. Hajjaj, T. Fukushima, Nat. Commun. 2016, 7, 12704.
- 10
- 10aA. B. Flynn, W. W. Ogilvie, Chem. Rev. 2007, 107, 4698;
- 10bA. Heumann, M. Réglier, Tetrahedron 1996, 52, 9289;
- 10cE. Negishi, Acc. Chem. Res. 1987, 20, 65.
- 11While it is well known that diarylacetylenes can be transformed into dibenzopentalenes through a catalytic dimerization reaction in N,N′-dimethylacetamide under the same reaction conditions without dibenzosiloles, the present reaction with dibenzosiloles in 1,2-dichloroethane did not result in the production of any corresponding by-products. For details of the synthesis of dibenzopentalenes from diarylacetylenes by the PdCl2/AgOTf/o-chloranil catalyst system, see:
- 11aT. Maekawa, Y. Segawa, K. Itami, Chem. Sci. 2013, 4, 2369;
- 11bT. Maekawa, H. Ueno, Y. Segawa, M. M. Haley, K. Itami, Chem. Sci. 2016, 7, 650.
- 12CCDC 1510553 (3 ka⋅0.5MeOH), 1510554 (3 la) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre.
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