Functionalized Contorted Polycyclic Aromatic Hydrocarbons by a One-Step Cyclopentannulation and Regioselective Triflyloxylation
M. Sc. Xuan Yang
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorM. Sc. Marvin Hoffmann
Theoretical and Computational Chemistry, Interdisciplinary Center for Scientific Computing (IWR), Ruprecht-Karls- Universität Heidelberg, Im Neuenheimer Feld 205A, 69120 Heidelberg, Germany
Search for more papers by this authorDr. Frank Rominger
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorM. Sc. Tobias Kirschbaum
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorProf. Dr. Andreas Dreuw
Theoretical and Computational Chemistry, Interdisciplinary Center for Scientific Computing (IWR), Ruprecht-Karls- Universität Heidelberg, Im Neuenheimer Feld 205A, 69120 Heidelberg, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Michael Mastalerz
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorM. Sc. Xuan Yang
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorM. Sc. Marvin Hoffmann
Theoretical and Computational Chemistry, Interdisciplinary Center for Scientific Computing (IWR), Ruprecht-Karls- Universität Heidelberg, Im Neuenheimer Feld 205A, 69120 Heidelberg, Germany
Search for more papers by this authorDr. Frank Rominger
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorM. Sc. Tobias Kirschbaum
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorProf. Dr. Andreas Dreuw
Theoretical and Computational Chemistry, Interdisciplinary Center for Scientific Computing (IWR), Ruprecht-Karls- Universität Heidelberg, Im Neuenheimer Feld 205A, 69120 Heidelberg, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Michael Mastalerz
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Search for more papers by this authorGraphical Abstract
Better than PAH: A highly regioselective bistriflyloxylation of a polycyclic aromatic hydrocarbon (PAH) occurs during its cyclopentannulation under Scholl-type conditions. OTf moieties undergo palladium-catalyzed cross-coupling reactions, allowing simple access to larger and more complex PAHs.
Abstract
The oxidative cyclodehydrogenation (often named the Scholl reaction) is still a powerful synthetic tool to construct even larger polycyclic aromatic hydrocarbons (PAHs) by multiple biaryl bond formations without the necessity of prior installation of reacting functional groups. Scholl-type reactions are usually very selective although the resulting products bear sometimes some surprises, such as the formation of five-membered instead of six-membered rings or the unexpected migration of aryl moieties. There are a few examples, where chlorinated byproducts were found when FeCl3 was used as reagent. To our knowledge, the direct functionalization of PAHs during Scholl-type cyclization by triflyloxylation has not been observed. Herein we describe the synthesis of functionalized PAHs by the formation of five-membered rings and a regioselective triflyloxylation in one step. The triflyloxylated PAHs can be used as reactants for further transformation to even larger contorted PAHs.
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References
- 1
- 1aY. Segawa, H. Ito, K. Itami, Nat. Rev. Mater. 2016, 1, 15002;
- 1bJ. C. Fetzer, W. R. Biggs, Polycyclic Aromat. Compd. 1994, 4, 3–17;
- 1cM. Müller, C. Kübel, K. Müllen, Chem. Eur. J. 1998, 4, 2099–2109;
10.1002/(SICI)1521-3765(19981102)4:11<2099::AID-CHEM2099>3.0.CO;2-T CAS Web of Science® Google Scholar
- 1dJ. Wu, W. Pisula, K. Müllen, Chem. Rev. 2007, 107, 718–747;
- 1eK. Müllen, ACS Nano 2014, 8, 6531–6541;
- 1fA. Narita, X.-Y. Wang, X. Feng, K. Müllen, Chem. Soc. Rev. 2015, 44, 6616–6643.
- 2O. V. Yazyev, Acc. Chem. Res. 2013, 46, 2319–2328.
- 3
- 3aK. Baumgärtner, F. Rominger, M. Mastalerz, Chem. Eur. J. 2018, 24, 8751–8755;
- 3bR. Yamaguchi, S. Hiroto, H. Shinokubo, Org. Lett. 2012, 14, 2472–2475;
- 3cR. Yamaguchi, S. Ito, B. S. Lee, S. Hiroto, D. Kim, H. Shinokubo, Chem. Asian J. 2013, 8, 178–190.
- 4
- 4aM. Grzybowski, K. Skonieczny, H. Butenschön, D. T. Gryko, Angew. Chem. Int. Ed. 2013, 52, 9900–9930; Angew. Chem. 2013, 125, 10084–10115;
- 4bR. Scholl, C. Seer, R. Weitzenböck, Ber. Dtsch. Chem. Ges. 1910, 43, 2202–2209.
- 5
- 5aY. Avlasevich, C. Kohl, K. Müllen, J. Mater. Chem. 2006, 16, 1053–1057;
- 5bK. Ota, T. Tanaka, A. Osuka, Org. Lett. 2014, 16, 2974–2977;
- 5cChaolumen, M. Murata, Y. Sugano, A. Wakamiya, Y. Murata, Angew. Chem. Int. Ed. 2015, 54, 9308–9312; Angew. Chem. 2015, 127, 9440–9444;
- 5dA. Naibi Lakshminarayana, J. Chang, J. Luo, B. Zheng, K.-W. Huang, C. Chi, Chem. Commun. 2015, 51, 3604–3607;
- 5eS. Kumar, M.-T. Ho, Y.-T. Tao, Org. Lett. 2016, 18, 200–203;
- 5fJ. Liu, A. Narita, S. Osella, W. Zhang, D. Schollmeyer, D. Beljonne, X. Feng, K. Müllen, J. Am. Chem. Soc. 2016, 138, 2602–2608;
- 5gJ. Liu, S. Osella, J. Ma, R. Berger, D. Beljonne, D. Schollmeyer, X. Feng, K. Müllen, J. Am. Chem. Soc. 2016, 138, 8364–8367;
- 5hChaolumen, M. Murata, A. Wakamiya, Y. Murata, Angew. Chem. Int. Ed. 2017, 56, 5082–5086; Angew. Chem. 2017, 129, 5164–5168;
- 5iS. Nobusue, K. Fujita, Y. Tobe, Org. Lett. 2017, 19, 3227–3230;
- 5jM. Kawamura, E. Tsurumaki, S. Toyota, Synthesis 2018, 02, 134–138;
- 5kL. J. Purvis, X. Gu, S. Ghosh, Z. Zhang, C. J. Cramer, C. J. Douglas, J. Org. Chem. 2018, 83, 1828–1841.
- 6
- 6aA. Pradhan, P. Dechambenoit, H. Bock, F. Durola, J. Org. Chem. 2013, 78, 2266–2274;
- 6bJ. M. Fernández-García, P. J. Evans, S. Medina Rivero, I. Fernández, D. García-Fresnadillo, J. Perles, J. Casado, N. Martín, J. Am. Chem. Soc. 2018, 140, 17188–17196;
- 6cK. Kawasumi, Q. Zhang, Y. Segawa, L. T. Scott, K. Itami, Nat. Chem. 2013, 5, 739.
- 7
- 7aY. Sakamoto, T. Suzuki, J. Am. Chem. Soc. 2013, 135, 14074–14077;
- 7bK. Y. Cheung, C. K. Chan, Z. Liu, Q. Miao, Angew. Chem. Int. Ed. 2017, 56, 9003–9007; Angew. Chem. 2017, 129, 9131–9135.
- 8
- 8aY. N. Oded, S. Pogodin, I. Agranat, J. Org. Chem. 2016, 81, 11389–11393;
- 8bM. S. Markoulides, C. Venturini, D. Neumeyer, A. Gourdon, New J. Chem. 2015, 39, 6498–6503.
- 9
- 9aH. Shinokubo, Proc. Jpn. Acad. Ser. B 2014, 90, 1–11;
- 9bG. Li, H. Phan, T. S. Herng, T. Y. Gopalakrishna, C. Liu, W. Zeng, J. Ding, J. Wu, Angew. Chem. Int. Ed. 2017, 56, 5012–5016; Angew. Chem. 2017, 129, 5094–5098;
- 9cQ. Chen, D. Wang, M. Baumgarten, D. Schollmeyer, K. Müllen, A. Narita, Chem. Asian J. 2019, 14, 1703–1707.
- 10Y.-Z. Tan, B. Yang, K. Parvez, A. Narita, S. Osella, D. Beljonne, X. Feng, K. Müllen, Nat. Commun. 2013, 4, 2646.
- 11P. Sarkar, P. Dechambenoit, F. Durola, H. Bock, Asian J. Org. Chem. 2012, 1, 366–376.
- 12Y. Yang, L. Yuan, B. Shan, Z. Liu, Q. Miao, Chem. Eur. J. 2016, 22, 18620–18627.
- 13
- 13aA. Pradhan, P. Dechambenoit, H. Bock, F. Durola, Angew. Chem. Int. Ed. 2011, 50, 12582–12585; Angew. Chem. 2011, 123, 12790–12793;
- 13bM. S. Little, S. G. Yeates, A. A. Alwattar, K. W. J. Heard, J. Raftery, A. C. Edwards, A. V. S. Parry, P. Quayle, Eur. J. Org. Chem. 2017, 1694–1703.
- 14
- 14aE. A. Bliss, R. J. Griffin, M. F. G. Stevens, J. Chem. Soc. Perkin Trans. 1 1987, 2217–2228;
- 14bR. A. Abramovitch, P. Chinnasamy, K. Evertz, G. Huttner, J. Chem. Soc. Chem. Commun. 1989, 3–5;
- 14cM. A. Castro, M. F. G. Stevens, J. Chem. Soc. Chem. Commun. 1992, 869–870.
- 15G. Zhang, F. Rominger, U. Zschieschang, H. Klauk, M. Mastalerz, Chem. Eur. J. 2016, 22, 14840–14845.
- 16X. Yang, F. Rominger, M. Mastalerz, Org. Lett. 2018, 20, 7270–7273.
- 17
- 17aK. Shiraishi, A. Rajca, M. Pink, S. Rajca, J. Am. Chem. Soc. 2005, 127, 9312–9313;
- 17bT. Fujikawa, Y. Segawa, K. Itami, J. Am. Chem. Soc. 2015, 137, 7763–7768;
- 17cV. Berezhnaia, M. Roy, N. Vanthuyne, M. Villa, J.-V. Naubron, J. Rodriguez, Y. Coquerel, M. Gingras, J. Am. Chem. Soc. 2017, 139, 18508–18511;
- 17dY. Zhu, Z. Xia, Z. Cai, Z. Yuan, N. Jiang, T. Li, Y. Wang, X. Guo, Z. Li, S. Ma, D. Zhong, Y. Li, J. Wang, J. Am. Chem. Soc. 2018, 140, 4222–4226.
- 18
- 18aB. Panda, T. K. Sarkar, Tetrahedron Lett. 2010, 51, 301–305;
- 18bJ. Cao, M. Miao, W. Chen, L. Wu, X. Huang, J. Org. Chem. 2011, 76, 9329–9337.
- 19
- 19aW. Dilthey, G. Hurtig, Ber. Dtsch. Chem. Ges. B 1934, 67, 495–496;
- 19bY. Zhu, X. Guo, Y. Li, J. Wang, J. Am. Chem. Soc. 2019, 141, 5511–5517.
- 20CCDC 1914188 (4), 1914189 (7), and 1914190 (15) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre.
