Synlett 2014; 25(17): 2429-2433
DOI: 10.1055/s-0034-1379140
letter
© Georg Thieme Verlag Stuttgart · New York

Toward Antikekulene: Angular 1,2-Di-, 2,3-Di-, and 1,2,15,16-Tetrachloro[6]phenylene

Alexandr Fonari
a  Department of Biology and Chemistry, New Mexico Highlands University, Las Vegas, NM 87701, USA
,
Jens C. Röder
b  Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460, USA   Fax: +1(510)6435208   Email: kpcv@berkeley.edu
,
Hao Shen
b  Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460, USA   Fax: +1(510)6435208   Email: kpcv@berkeley.edu
,
Tatiana V. Timofeeva
a  Department of Biology and Chemistry, New Mexico Highlands University, Las Vegas, NM 87701, USA
,
K. Peter C. Vollhardt*
b  Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460, USA   Fax: +1(510)6435208   Email: kpcv@berkeley.edu
› Author Affiliations
Further Information

Publication History

Received: 16 June 2014

Accepted after revision: 20 August 2014

Publication Date:
17 September 2014 (online)


Abstract

The synthesis of the first ring-functionalized heliphenes is described, comprised of angular 1,2-di-, 2,3-di-, and 1,2,15,16-tetrachloro[6]phenylene, via a series of Sonogashira couplings and cobalt-catalyzed alkyne cyclotrimerization steps. These molecules are explored as potential precursors to antikekulene and their reactivity compared to that of the parent angular [6]phenylene. An X-ray structural determination of 1,2,15,16-tetrachloro[6]phenylene reveals a structure with a considerably larger helical separation than in [6]phenylene, caused by the bulk of the appended chlorine atoms.

Supporting Information

 
  • References and Notes

    • 1a For a review of the [N]phenylenes, see: Miljanić OŠ, Vollhardt KP. C. In Carbon Rich Compounds: Molecules to Materials . Haley MM, Tykwinski RR. Wiley-VCH; Weinheim: 2005: 140

    • For recent work, see, for example:
    • 1b Gu Z, Vollhardt KP. C. Synthesis 2013; 45: 2469
    • 1c Gu Z, Boursalian GB, Gandon V, Padilla R, Shen H, Timofeeva TV, Tongwa P, Vollhardt KP. C, Yakovenko AA. Angew. Chem. Int. Ed. 2011; 50: 9413
    • 1d González Gómez JA, Green J, Vollhardt KP. C. Synlett 2011; 805
    • 1e Engelhardt V, Garcia JG, Hubaud AA, Lyssenko KA, Spyroudis S, Timofeeva TV, Tongwa P, Vollhardt KP. C. Synlett 2011; 280
    • 1f Mohler DL, Kumaraswamy S, Stanger A, Vollhardt KP. C. Synlett 2006; 2981

      For a selection of recent computational treatments, see
    • 2a Luzanov AV. J. Struct. Chem. 2013; 54: 277
    • 2b Dickens TK, Mallion RB. Chem. Phys. Lett. 2011; 517: 98
    • 2c Randić M, Balaban AT, Plavšic D. Phys. Chem. Chem. Phys. 2011; 13: 20644
    • 2d Aihara J. J. Phys. Chem. A 2008; 112: 4382
    • 2e Schulman JM, Disch RL. J. Phys. Chem. A 2007; 111: 10010
  • 3 Eickmeier C, Junga H, Matzger AJ, Scherhag F, Shim M, Vollhardt KP. C. Angew. Chem., Int. Ed. Engl. 1997; 36: 2103
    • 4a Han S, Bond AD, Disch RL, Holmes D, Schulman JM, Teat SJ, Vollhardt KP. C, Whitener GD. Angew. Chem. Int. Ed. 2002; 41: 3223
    • 4b Han S, Anderson DR, Bond AD, Chu HV, Disch RL, Holmes D, Schulman JM, Teat SJ, Vollhardt KP. C, Whitener GD. Angew. Chem. Int. Ed. 2002; 41: 3227
  • 5 We thank Professor Thomas Drewello, University of Erlangen-Nürnberg, for providing preliminary data.
  • 6 For a similar fragmentation of hexahelicene, see: Dougherty RC. J. Am. Chem. Soc. 1968; 90: 5788
    • 7a FVP of angular [4]phenylene causes isomerization to ‘biphenylene dimer’: Dosa PI, Gu Z, Hager D, Karney WL, Vollhardt KP. C. Chem. Commun. 2009; 45: 1967

    • For related reactions of angular and linear [3]phenylene, see:
    • 7b Matzger AJ, Vollhardt KP. C. Chem. Commun. 1997; 33: 1415
    • 7c Dosa PI, Schleifenbaum A, Vollhardt KP. C. Org. Lett. 2001; 3: 1017
  • 8 Grzybowski M, Skonieczny K, Butenschön H, Gryko DT. Angew. Chem. Int. Ed. 2013; 52: 9900
  • 9 For a recent review, see: Hierso J.-C, Beaupérin M, Saleh S, Job A, Andrieu J, Picquet M. C. R. Chim. 2013; 16: 580
  • 10 For the successful employment of chloroarenes in CpCo-catalyzed cyclizations, see: Berris BC, Hovakeemian GH, Lai Y.-H, Mestdagh H, Vollhardt KP. C. J. Am. Chem. Soc. 1985; 107: 5670
  • 11 Nicolaou KC, Dai WM, Hong YP, Baldridge KK, Siegel JS, Tsay SC. J. Am. Chem. Soc. 1993; 115: 7944
  • 12 Schmidt-Radde RH, Vollhardt KP. C. J. Am. Chem. Soc. 1992; 114: 9713
    • 13a Tsefrikas VM, Scott LT. Chem. Rev. 2006; 106: 4868
    • 13b Brooks MA, Scott LT. J. Am. Chem. Soc. 1999; 121: 5444
    • 14a Chiusoli GP, Catellani M, Costa M, Motti E, Della Ca’ N, Maestri G. Coord. Chem. Rev. 2010; 254: 456
    • 14b Livendahl M, Echavarren AM. Isr. J. Chem. 2010; 50: 630
    • 14c McGlacken GP, Bateman LM. Chem. Soc. Rev. 2009; 38: 2447
  • 15 Shi F, Larock RC. Top. Curr. Chem. 2010; 292: 123

    • For NMR data of sexiphenyls, see:
    • 17a Mathew SM, Engle JT, Ziegler CJ, Hartley CS. J. Am. Chem. Soc. 2013; 135: 6714
    • 17b Mathew SM, Hartley CS. Macromolecules 2011; 44: 8425
    • 17c Ozasa S, Fujioka Y, Ibuki E. Chem. Pharm. Bull. 1982; 30: 2698
    • 17d Ibuki E, Ozasa S, Fujioka Y, Okada M, Yanagihara Y. Chem. Pharm. Bull. 1982; 30: 2369
  • 18 Chinchilla R, Nájera C. Chem. Rev. 2007; 107: 874
  • 19 Shen H, Vollhardt KP. C. Synlett 2012; 23: 208
  • 20 Lo Sterzo C. Synlett 1999; 1704

    • Patterned after:
    • 21a Schmidt-Radde RH, Vollhardt KP. C. J. Am. Chem. Soc. 1992; 114: 9713
    • 21b Hillard RL. III, Vollhardt KP. C. Angew. Chem., Int. Ed. Engl. 1977; 16: 399
  • 22 CCDC 778109 contains the supplementary crystallographic data for 2d. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
  • 23 Bondi A. J. Phys. Chem. 1964; 68: 441
  • 24 Holmes D, Kumaraswamy S, Matzger AJ, Vollhardt KP. C. Chem. Eur. J. 1999; 5: 3399

    • For selected reviews, see:
    • 25a Everson DA, Weix DJ. J. Org. Chem. 2014; 79: 4793
    • 25b Nelson TD, Crouch RD. Org. React. 2004; 63: 265
  • 26 See, for example: Colon I, Kelsey DR. J. Org. Chem. 1986; 51: 2627
  • 27 Rieke RD, Rhyne LD. J. Org. Chem. 1979; 44: 3445
  • 28 See, for example: Fulmer GR, Miller AJ. M, Sherden NH, Gottlieb HE, Nudelman A, Stoltz BM, Bercaw JE, Goldberg KI. Organometallics 2010; 29: 2176
  • 29 For a recent review of the properties and applications of helicenes, see: Gingras M. Chem. Soc. Rev. 2013; 42: 1051