Functionalization of Azapentabenzocorannulenes by Fivefold C−H Borylation and Cross-Coupling Arylation: Application to Columnar Liquid-Crystalline Materials
Taro Nagano
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 Japan
Search for more papers by this authorKimihiro Nakamura
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 Japan
Search for more papers by this authorYuki Tokimaru
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Shingo Ito
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371 Singapore
Search for more papers by this authorDr. Daigo Miyajima
RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama, 351-0198 Japan
Search for more papers by this authorProf. Dr. Takuzo Aida
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 Japan
RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama, 351-0198 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Kyoko Nozaki
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 Japan
Search for more papers by this authorTaro Nagano
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 Japan
Search for more papers by this authorKimihiro Nakamura
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 Japan
Search for more papers by this authorYuki Tokimaru
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Shingo Ito
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371 Singapore
Search for more papers by this authorDr. Daigo Miyajima
RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama, 351-0198 Japan
Search for more papers by this authorProf. Dr. Takuzo Aida
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 Japan
RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama, 351-0198 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Kyoko Nozaki
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 Japan
Search for more papers by this authorGraphical Abstract
One-shot fivefold regioselective functionalization of azapentabenzocorannulene by iridium-catalyzed fivefold C−H borylation and Suzuki–Miyaura cross-coupling reactions is reported. The present method expands the variety and utility of azapentabenzocorannulenes as promising π-conjugated cores (see scheme).
Abstract
Herein, the one-shot fivefold functionalization of azapentabenzocorannulenes by an iridium-catalyzed fivefold C−H borylation reaction that exhibits excellent regioselectivity is reported. The borylated product can be used as a versatile synthetic intermediate for further derivatization via Suzuki–Miyaura cross-coupling reactions. This fivefold borylation/arylation sequence was employed to synthesize liquid-crystalline azapentabenzocorannulenes with five 3,4,5-trialkoxyphenyl groups, which assemble into 1D hexagonal columnar structures over a wide temperature range. The present method expands the variety and utility of azapentabenzocorannulenes as promising π-conjugated cores.
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References
- 1For reviews, see:
- 1aY.-T. Wu, J. S. Siegel, Chem. Rev. 2006, 106, 4843–4867;
- 1bV. M. Tsefrikas, L. T. Scott, Chem. Rev. 2006, 106, 4868–4884;
- 1cS. Higashibayashi, H. Sakurai, Chem. Lett. 2011, 40, 122–128;
- 1dA. Sygula, Eur. J. Org. Chem. 2011, 1611–1625;
- 1eT. Amaya, T. Hirao, Chem. Commun. 2011, 47, 10524–10535;
- 1fM. Saito, H. Shinokubo, H. Sakurai, Mater. Chem. Front. 2018, 2, 635–661;
- 1gE. Nestoros, M. C. Stuparu, Chem. Commun. 2018, 54, 6503–6519.
- 2For reviews, see:
- 2aT. Ishiyama, N. Miyaura, J. Organomet. Chem. 2003, 680, 3–11;
- 2bN. Miyaura, Bull. Chem. Soc. Jpn. 2008, 81, 1535–1553;
- 2cI. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J. M. Murphy, J. F. Hartwig, Chem. Rev. 2010, 110, 890–931;
- 2dJ. F. Hartwig, Chem. Soc. Rev. 2011, 40, 1992–2002;
- 2eJ. F. Hartwig, Acc. Chem. Res. 2012, 45, 864–873;
- 2fJ. F. Hartwig, M. A. Larsen, ACS Cent. Sci. 2016, 2, 281–292;
- 2gE. C. Neeve, S. J. Geier, I. A. I. Mkhalid, S. A. Westcott, T. B. Marder, Chem. Rev. 2016, 116, 9091–9161;
- 2hL. Xu, G. Wang, S. Zhang, H. Wang, L. Wang, L. Liu, J. Jiao, P. Li, Tetrahedron 2017, 73, 7123–7157.
- 3For reviews, see:
- 3aH. Shinokubo, Proc. Jpn. Acad. Ser. B 2014, 90, 1–11;
- 3bY. Segawa, T. Maekawa, K. Itami, Angew. Chem. Int. Ed. 2015, 54, 66–81;
Angew. Chem. 2015, 127, 68–83;
10.1002/ange.201403729 Google Scholar
- 3cA. Narita, X.-Y. Wang, X. Feng, K. Müllen, Chem. Soc. Rev. 2015, 44, 6616–6643.
- 4
- 4aR. Yamaguchi, S. Hiroto, H. Shinokubo, Org. Lett. 2012, 14, 2472–2475;
- 4bR. Yamaguchi, S. Ito, B. S. Lee, S. Hiroto, D. Kim, H. Shinokubo, Chem. Asian J. 2013, 8, 178–190;
- 4cK. Oda, S. Hiroto, I. Hisaki, H. Shinokubo, Org. Biomol. Chem. 2017, 15, 1426–1434.
- 5
- 5aM. N. Eliseeva, L. T. Scott, J. Am. Chem. Soc. 2012, 134, 15169–15172;
- 5bK. Kawasumi, Q. Zhang, Y. Segawa, L. T. Scott, K. Itami, Nat. Chem. 2013, 5, 739–744.
- 6
- 6aH. Hata, H. Shinokubo, A. Osuka, J. Am. Chem. Soc. 2005, 127, 8264–8265;
- 6bS. Hiroto, Y. Miyake, H. Shinokubo, Chem. Rev. 2017, 117, 2910–3043. See also:
- 6cS. Shimizu, Chem. Rev. 2017, 117, 2730–2784.
- 7
- 7aD. N. Coventry, A. S. Batsanov, A. E. Goeta, J. A. K. Howard, T. B. Marder, R. N. Perutz, Chem. Commun. 2005, 2172–2174;
- 7bA. G. Crawford, Z. Liu, I. A. I. Mkhalid, M.-H. Thibault, N. Schwarz, G. Alcaraz, A. Steffen, J. C. Collings, A. S. Batsanov, J. A. K. Howard, T. B. Marder, Chem. Eur. J. 2012, 18, 5022–5035;
- 7cZ. Liu, Y. Wang, Y. Chen, J. Liu, Q. Fang, C. Kleeberg, T. B. Marder, J. Org. Chem. 2012, 77, 7124–7128;
- 7dL. Ji, K. Fucke, S. K. Bose, T. B. Marder, J. Org. Chem. 2015, 80, 661–665.
- 8
- 8aT. Teraoka, S. Hiroto, H. Shinokubo, Org. Lett. 2011, 13, 2532–2535;
- 8bG. Battagliarin, C. Li, V. Enkelmann, K. Müllen, Org. Lett. 2011, 13, 3012–3015;
- 8cS. Ito, S. Hiroto, H. Shinokubo, Chem. Lett. 2014, 43, 1309–1311.
- 9
- 9aT. Kimoto, K. Tanaka, Y. Sakai, A. Ohno, K. Yoza, K. Kobayashi, Org. Lett. 2009, 11, 3658–3661;
- 9bR. Ozawa, K. Yoza, K. Kobayashi, Chem. Lett. 2011, 40, 941–943;
- 9cY. Takaki, K. Yoza, K. Kobayashi, Chem. Lett. 2017, 46, 655–658.
- 10
- 10aH. Nishimura, M. N. Eliseeva, A. Wakamiya, L. T. Scott, Synlett 2015, 26, 1578–1580;
- 10bH. Nishimura, N. Ishida, A. Shimazaki, A. Wakamiya, A. Saeki, L. T. Scott, Y. Murata, J. Am. Chem. Soc. 2015, 137, 15656–15659.
- 11S. Ito, Y. Tokimaru, K. Nozaki, Angew. Chem. Int. Ed. 2015, 54, 7256–7260;
Angew. Chem. 2015, 127, 7364–7368.
10.1002/ange.201502599 Google Scholar
- 12
- 12aH. Yokoi, Y. Hiraoka, S. Hiroto, D. Sakamaki, S. Seki, H. Shinokubo, Nat. Commun. 2015, 6, 8215;
- 12bH. Yokoi, S. Hiroto, D. Sakamaki, S. Seki, H. Shinokubo, Chem. Sci. 2018, 9, 819–824;
- 12cH. Yokoi, S. Hiroto, H. Shinokubo, J. Am. Chem. Soc. 2018, 140, 4649–4655;
- 12dM. Takeda, S. Hiroto, H. Yokoi, S. Lee, D. Kim, H. Shinokubo, J. Am. Chem. Soc. 2018, 140, 6336–6342.
- 13It should be noted that “corannulene” is not included in the list of retained names for polycyclic hydrocarbons; the preferred IUPAC name is 3a2-azadibenzo[fg,ij]benzo[5,6]acenaphtho[4,3,2,1,8,7-pqrstuv]pentaphene.
- 14See also: V. M. Tsefrikas, A. K. Greene, L. T. Scott, Org. Chem. Front. 2017, 4, 688–698.
- 15See also: Y. Tokimaru, S. Ito, K. Nozaki, Angew. Chem. Int. Ed. 2018, 57, 9818–9822;
Angew. Chem. 2018, 130, 9966–9970.
10.1002/ange.201805678 Google Scholar
- 16For details, see the Supporting Information.
- 17H. Sakurai, T. Daiko, H. Sakane, T. Amaya, T. Hirao, J. Am. Chem. Soc. 2005, 127, 11580–11581.
- 18In this context, we propose that azapentabenzocorannulene, which has a larger π-conjugated system than corannulene and sumanene, should similarly afford bowl-in-bowl-type 1D columnar liquid crystals. Indeed, tBu-substituted 1 a and H-substituted 1 e adopt a bowl-in-bowl stacking structure in their single crystals, as shown in our previous report (see Ref. [11]) and Figure 2.
- 19
- 19aS. Sergeyev, W. Pisula, Y. A. Geerts, Chem. Soc. Rev. 2007, 36, 1902–1929;
- 19bT. Wöhrle, I. Wurzbach, J. Kirres, A. Kostidou, N. Kapernaum, J. Litterscheidt, J. C. Haenle, P. Staffeld, A. Baro, F. Giesselmann, S. Laschat, Chem. Rev. 2016, 116, 1139–1241.
- 20
- 20aD. Miyajima, K. Tashiro, F. Araoka, H. Takezoe, J. Kim, K. Kato, M. Takata, T. Aida, J. Am. Chem. Soc. 2009, 131, 44–45;
- 20bM. Mattarella, J. M. Haberl, J. Ruokolainen, E. M. Landau, R. Mezzenga, J. S. Siegel, Chem. Commun. 2013, 49, 7204–7206;
- 20cY. Shoji, T. Kajitani, F. Ishiwari, Q. Ding, H. Sato, H. Anetai, T. Akutagawa, H. Sakurai, T. Fukushima, Chem. Sci. 2017, 8, 8405–8410.
- 21For reviews, see:
- 21aH. Takezoe, K. Kishikawa, E. Gorecka, J. Mater. Chem. 2006, 16, 2412–2416;
- 21bR. J. Bushby, N. Boden, In Handbook of Liquid Crystals, 2nd ed., Vol. 4, Wiley-VCH, Weinheim, 2014, pp. 569–601;
- 21cH. Takezoe, Mol. Cryst. Liq. Cryst. 2017, 646, 46–65.
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