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

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.

Key words

alkynes - cobalt - cycloaddition - helical structures - polycycles

• 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 the hydrogenolysis of biphenylenes, see:
• 16a Edelbach BL, Vicic DA, Lachicotte RJ, Jones WD. Organometallics 1998; 17: 4784; and references cited therein

For a monograph, see:
• 16b Shepherd MK. Cyclobutarenes . Elsevier; Amsterdam: 1991

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