Synlett 2016; 27(14): 2091-2094
DOI: 10.1055/s-0035-1562510
cluster
© Georg Thieme Verlag Stuttgart · New York

Studies toward the Synthesis of Hepta-peri-heptabenzo-[7]circulene

Xuejin Yang
a   Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, P. R. of China   Email: miaoqian@cuhk.edu.hk
,
Qian Miao*
a   Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, P. R. of China   Email: miaoqian@cuhk.edu.hk
b   Center of Novel Functional Molecules, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, P. R. of China
› Author Affiliations
Further Information

Publication History

Received: 25 April 2016

Accepted after revision: 31 May 2016

Publication Date:
05 July 2016 (online)


Abstract

In this letter we report the synthesis and characterization of two new heptagon-embedded nonplanar π-conjugated molecules, which can be regarded as synthetic precursors of hepta-peri-heptabenzo-[7]circulene, an interesting but unknown polycyclic arene with negative curvature.

Supporting Information

 
  • References and Notes

  • 1 Rieger R, Müllen K. J. Phys. Org. Chem. 2010; 23: 315
    • 2a Yamamoto K, Harada T, Nakazaki M, Naka T, Kai Y, Harada S, Kasai N. J. Am. Chem. Soc. 1983; 105: 7171
    • 2b Yamamoto K, Harada T, Okamoto Y, Chikamatsu H, Nakazaki M, Kai Y, Nakao T, Tanaka M, Harada S, Kasai N. J. Am. Chem. Soc. 1988; 110: 3578
  • 3 Kawasumi K, Zhang Q, Segawa Y, Scott LT, Itami K. Nat. Chem. 2013; 5: 739
  • 4 Cheung KY, Xu X, Miao Q. J. Am. Chem. Soc. 2015; 137: 3910
    • 5a Mughal EU, Kuck D. Chem. Commun. 2012; 48: 8880
    • 5b Pradhan A, Dechambenoit P, Bock H, Durola F. J. Org. Chem. 2013; 78: 2266
  • 6 Cheung KY, Miao Q In Polycyclic Arenes and Heteroarenes: Synthesis, Properties and Applications . Miao Q. Wiley-VCH; Weinheim: 2016. Chap. 1, 85
  • 7 Chuang C, Fan Y.-C, Jin B.-Y. J. Chem. Inf. Model. 2009; 49: 361
  • 8 Beuerle F, Herrmann C, Whalley AC, Valente C, Gamburd A, Ratner MA, Stoddart JF. Chem. Eur. J. 2011; 17: 3868
  • 9 Lenosky T, Gonze X, Teter M, Elser V. Nature (London, U.K.) 1992; 355: 333
  • 10 Townsend SJ, Lenosky TJ, Muller DA, Nichols CS, Elser V. Phys. Rev. Lett. 1992; 69: 921
  • 11 Stabel A, Herwig P, Müllen K, Rabe JP. Angew. Chem., Int. Ed. Engl. 1995; 34: 1609
  • 12 Wu J, Pisula W, Müllen K. Chem. Rev. 2007; 107: 718
  • 13 Sasaki T, Kanematsu K, Iizuka K. J. Org. Chem. 1976; 41: 1105
  • 14 Zhai L, Shukla R, Rathore R. Org. Lett. 2009; 11: 3474
  • 15 Luo J, Xu X, Mao R, Miao Q. J. Am. Chem. Soc. 2012; 134: 13796
  • 16 King BT, Kroulik J, Robertson CR, Rempala P, Hilton CL, Korinek JD, Gortari LM. J. Org. Chem. 2007; 72: 2279
  • 17 Synthesis of 6b A mixture of compound 5b (0.25 g, 0.50 mmol) and diphenylcyclopropenone (4, 0.21 g, 1.0 mmol) in toluene (12 mL) was heated under an atmosphere of N2 at reflux for about 4 d. The solution was concentrated under a reduced pressure, and the crude product was purified by silica gel column chromatography using hexane–EtOAc (4:1) as eluent yielding 0.22 g (0.32 mmol, 64%) of 6b as a white solid; mp 267.6–269.7 °C. 1H NMR (400 MHz, CD2Cl2): δ = 8.67 (d, 3 J = 8.1 Hz, 2 H), 8.06 (dd, 3 J = 8.4 Hz, 4 J = 0.8 Hz, 2 H), 7.57 (t, 3 J = 7.0, 4 J = 1.2 Hz, 2 H), 7.33 (t, 3 J = 7.3 Hz, 4 J = 1.1 Hz, 2 H), 7.18–7.20 (m, 4 H), 7.06–7.12 (m, 6 H), 6.22–6.25 (m, 6 H), 3.48 (s, 12 H). 13C NMR (100 MHz, CDCl3): δ = 199.4, 160.5, 146.5, 142.3, 135.30, 135.27, 133.9, 130.9, 130.2, 129.9, 129.6, 128.1, 127.8, 126.9, 126.2, 122.5, 108.6, 99.9, 55.2. HRMS (ESI+): m/z calcd for C47H36O5 [M + Na]+: 703.2455; found: 703.2468. Synthesis of 10 A solution of 6b (34.0 mg, 0.0499 mmol) in anhydrous CH2Cl2 (50 mL) was bubbled with N2 for 10 min. Then a solution of FeCl3 (243 mg, 1.50 mmol, 30 equiv) in MeNO2 (1.3 mL), which was also bubbled with N2 for 10 min, was added to the above solution at 0 °C dropwise. The resulting black solution was stirred at 0 °C with a stream of N2 bubbled through it for about 15 min. The reaction was quenched by addition of 1 mL of MeOH, and the mixture was treated with water. The aqueous phase was extracted with CH2Cl2, and the combined organic layers were washed with a sat. NaHCO3 aqueous solution, brine, dried over anhydrous Na2SO4 and then concentrated under reduced pressure. The dark red crude product was purified by column chromatography on silica gel using CH2Cl2–hexane (1:1, v/v) as eluent. Compound 10 (25.6 mg, 0.0381 mmol) was obtained as orange red powder in a yield of 75%; mp >350 °C. 1H NMR (400 MHz, CDCl3): δ = 9.51–9.54 (m, 2 H), 8.78–8.81 (m, 2 H), 8.68 (d, 3 J = 7.6 Hz, 2 H), 8.64 (d, 3J = 8.0 Hz, 2 H), 7.81 (t, 3 J = 7.8 Hz, 2 H), 7.63–7.66 (m, 4 H), 7.04 (s, 2 H), 4.15 (s, 6 H), 4.03 (s, 6 H). 13C NMR (100 MHz, C2D2Cl4): δ = 198.0, 158.2, 156.1, 136.6, 130.1, 129.3, 128.4, 128.2, 128.0, 127.7, 127.2, 126.9, 125.7, 125.3, 125.14, 125.05, 124.9, 122.7, 119.1, 113.1, 111.3, 97.1, 56.2, 56.1. HRMS (ESI+): m/z calcd for C47H28O5 [M + H]+: 673.2010; found: 673.2012.
    • 18a Ferreira EM, Zhang H, Stolz BM In The Mizoroki Heck Reaction . Oestreich M. Wiley; Chichester: 2009. Chap. 9,; 34
    • 18b Itahara T. J. Org. Chem. 1985; 50: 5546
    • 18c Jia C, Lu W, Kitamura T, Fujiwara Y. Org. Lett. 1999; 1: 2097
    • 18d Jones RC, Gałęzowski M, O’Shea DF. J. Org. Chem. 2013; 78: 8044
  • 19 Anslyn EV, Dougherty DA. Modern Physical Organic Chemistry . University Science Books; Sausalito: 2004. Chap. 1, 22