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Synlett 2004(1): 177-181  
DOI: 10.1055/s-2003-43335
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© Georg Thieme Verlag Stuttgart · New York

Synthesis of Functionalized Carbon-Sulfur [5]Helicene: Pd-Catalyzed Negishi Cross-Coupling Between the β-Positions of Thiophenes

Makoto Miyasaka, Andrzej Rajca*
Department of Chemistry, University of Nebraska, Lincoln, NE 68588-0304, USA
Fax: +1(402)4729204; e-Mail: arajca1@unl.edu;
Further Information

Publication History

Received 31 August 2003
Publication Date:
26 November 2003 (online)

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Abstract

Octyl- and bromo-substituted carbon-sulfur [5]helicene was prepared in several steps starting from either thiophene or 3-bromothiophene. Pd-catalyzed Negishi cross-coupling between the β-positions of thiophenes was one of the key steps in the synthesis.

Key words

helical structures - cross-coupling - alkylthiophene - ­helicene - oligothiophene

    References

  • 1a Newman MS. Lutz WB. Lednicer D. J. Am. Chem. Soc.  1955,  77:  3420 
    CrossrefGoogle Scholar
  • 1b Newman MS. Lednicer D. J. Am. Chem. Soc.  1956,  78:  4765 
    CrossrefGoogle Scholar
  • 2 Martin RH. Angew. Chem., Int. Ed. Engl.  1974,  13:  649 
    CrossrefGoogle Scholar
  • 3a Fuchs W. Niszel F. Chem. Ber.  1927,  60:  209 
    Google Scholar
  • 3b Zander M. Franke WH. Chem. Ber.  1969,  102:  2729 
    Google Scholar
  • 4a Urbano A. Angew. Chem. Int. Ed.  2003,  42:  3986 
    CrossrefGoogle Scholar
  • 4b Schmuck C. Angew. Chem. Int. Ed.  2003,  42:  2448 
    CrossrefGoogle Scholar
  • 5a Nuckolls C. Katz TJ. Katz G. Collings PJ. Castellanos L. J. Am. Chem. Soc.  1999,  121:  79 
    CrossrefGoogle Scholar
  • 5b Paruch K. Vyklicky L. Katz TJ. Incarvito CD. Rheingold AL. J. Org. Chem.  2000,  65:  8774 
    CrossrefGoogle Scholar
  • 6a Verbiest T. Van Elshocht S. Kauranen M. Hellemans L. Snauwaert J. Nuckolls C. Katz TJ. Persoons A. Science  1998,  282:  913 
    CrossrefGoogle Scholar
  • 6b Fox JM. Katz TJ. Elshocht SV. Verbiest T. Kauranen M. Persoons A. Thongpanchang T. Krauss T. Brus L. J. Am. Chem. Soc.  1999,  121:  3453 
    CrossrefGoogle Scholar
  • 7a Han S. Bond AD. Disch RL. Holmes D. Schulman JM. Teat SJ. Vollhardt KPC. Whitener GD. Angew. Chem. Int. Ed.  2002,  41:  3223 
    CrossrefGoogle Scholar
  • 7b Han S. Anderson DR. Bond AD. Chu HV. Disch RL. Holmes D. Schulman JM. Teat SJ. Vollhardt KPC. Whitener GD. Angew. Chem. Int. Ed.  2002,  41:  3227 
    CrossrefGoogle Scholar
  • 8 Field JE. Hill TJ. Venkataraman D. J. Org. Chem.  2003,  68:  6071 
    CrossrefGoogle Scholar
  • 9 Teply F. Stara IG. Stary I. Kollarovic A. Saman D. Vyskocil S. Fiedler P. J. Org. Chem.  2003,  68:  5193 
    CrossrefGoogle Scholar
  • 10 Wachsmann C. Weber E. Czugler M. Seichter W. Eur. J. Org. Chem.  2003,  2863 
    CrossrefGoogle Scholar
  • 11 Eliel EL. Wilen SH. Stereochemistry of Organic Compounds   Wiley; New York: 1994. 
    Google Scholar
  • 12 Herman WN. J. Opt. Soc. Am. A  2001,  18:  2806 
    Google Scholar
  • 13 Miyamoto Y. Rubio A. Cohen ML. Phys. Rev. B  1999,  60:  13885 
    CrossrefGoogle Scholar
  • Oligothiophenes:
  • 14a Roncali J. Acc. Chem. Res.  2000,  33:  147 
    CrossrefGoogle Scholar
  • 14b Fichou D. J. Mater. Chem.  2000,  10:  571 
    CrossrefGoogle Scholar
  • Carbon-sulfur allotropic forms:
  • 15a Lee AWM. Yeung ABW. Yuen MSM. Zhang H. Zhao X. Wong WY. Chem. Commun.  2000,  75 
    Google Scholar
  • 15b Frapper G. Saillard J.-Y. J. Am. Chem. Soc.  2000,  122:  5367 
    Google Scholar
  • 15c Genin H. Hoffmann R. J. Am. Chem. Soc.  1995,  117:  12328 
    Google Scholar
  • 15d Chou J.-H. Rauchfuss TB. Z. Naturforsch. B: Chem. Sci  1997,  52:  1549 
    Google Scholar
  • 16 Meurer PP. Vögtle F. Top. Curr. Chem.  1985,  127:  1 
    Google Scholar
  • Thiophene-based helicenes:
  • 17a Phillips KES. Katz TJ. Jockusch S. Lovinger AJ. Turro NJ. J. Am. Chem. Soc.  2001,  123:  11899 
    CrossrefGoogle Scholar
  • 17b Yamada K. Kobori Y. Nakagawa H. Chem. Commun.  2000,  97 
    CrossrefGoogle Scholar
  • 17c Tanaka K. Osuga H. Suzuki H. Shogase Y. Kitahara Y. J. Chem. Soc., Perkin Trans. 1  1998,  935 
    CrossrefGoogle Scholar
  • 17d Larsen J. Bechgaard K. J. Org. Chem.  1996,  61:  1151 
    CrossrefGoogle Scholar
  • 17e Yamada K. Ogashiwa S. Tanaka H. Nakagawa H. Kawazura H. Org. Lett.  1981,  343 
    CrossrefGoogle Scholar
  • 17f Wynberg H. Acc. Chem. Res.  1971,  4:  65 
    CrossrefGoogle Scholar
  • 18 Rajca A. Wang H. Pink M. Rajca S. Angew. Chem. Int. Ed.  2000,  39:  4481 
    CrossrefGoogle Scholar
  • 19 Determination of the absolute configuration of 1 by vibrational circular dichroism spectroscopy: Friedmann TB. Cao X. Wang H. Rajca A. Nafie LA. J. Phys. Chem. A  2003,  107:  7692 
    CrossrefGoogle Scholar
  • 20 Synthesis of 4-bromo-2-octylthiophene 7 from propargyl bromide via acid-catalyzed cyclization of acetylenic ketones: Masquelin T. Obrecht D. Tetrahedron Lett.  1994,  35:  9387 
    CrossrefGoogle Scholar
  • 21 3-Bromo-2-trimethylsilylthiophene may also be prepared in 87% yield from 2,3-dibromothiophene: Deffieux D. Bonafoux D. Bordeau M. Biran C. Dunogues J. Organometallics  1996,  15:  2041 
    CrossrefGoogle Scholar
  • 22 Weinreb amide: Nahm S. Weinreb SM. Tetrahedron Lett.  1981,  22:  3815 
    CrossrefGoogle Scholar
  • 24 NaBH4/AlCl3: Ono A. Suzuki N. Kamimura J. Synthesis  1987,  736 
    Article in Thieme ConnectGoogle Scholar
  • 25 t-BuOK-mediated alkylation: Brandsma L. Mal’kina AG. Lochman L. von Schleyer PR. Recl. Trav. Chim. Pays-Bas  1994,  113:  529 
    Google Scholar
  • 26 2-Octylthiophene may also be prepared by reaction of iodine with ate complexes of trioctylborane and 2-thienyllithium: Sotoyama T. Hara S. Suzuki A. Bull. Chem. Soc. Jpn.  1979,  52:  1865 
    Google Scholar
  • 27 Bromination of 2-octylthiophene: Pabst GR. Pfuller OC. Sauer J. Tetrahedron  1999,  55:  8045 
    CrossrefGoogle Scholar
  • 28 Halogen migration: Gronowitz S. Holm B. Acta Chem. Scand.  1969,  2207 
    Google Scholar
  • 29 Dai C. Fu GC. J. Am. Chem. Soc.  2001,  123:  2719 
    CrossrefPubMedGoogle Scholar
  • 33a

    Allylic coupling of J = 1 Hz is also observed in thiophenes 6 and 7.

  • 33b

    The downfield shift for the β-proton in dilithiated 14 relative to the monolithiated 14 is found as well (Figure [2] ).

  • 35 Rajca A. Wang H. Bolshov P. Rajca S. Tetrahedron  2001,  57:  3725 
    CrossrefGoogle Scholar
  • 36 Rajca A. Safronov A. Rajca S. Wongsriratanakul J. J. Am. Chem. Soc.  2000,  122:  3351 
    CrossrefGoogle Scholar
  • 37 Yamada K. Nakagawa H. Kawazura H. Bull. Chem. Soc. Jpn.  1986,  59:  2429 
    Google Scholar
  • 38a

    3,3¢-Bithianaphthenyl 19: mp 82-83 °C (lit mp 82.7-83.0 °C).
    Crossref
  • 38b Wynberg H. Cabell M. J. Org. Chem.  1973,  38:  2814 ; these authors report 72% yield of ‘pink solid’ of 19, prior to column chromatography and recrystallization
    CrossrefGoogle Scholar
23

Attempts at direct alkylation of α-metallated 4 with 1-bromooctane resulted in either negligible extent of conversion and/or migration of the TMS group with alkylation at the α-position adjacent to the bromine.

30

LDA is added to 13 in Et2O.

31

Upon the resolution enhancement (exponential line broadening, LB = -1.20 Hz, and Gaussian broadening, GB = +0.30 Hz) of the 1H NMR spectra for Li 1 , the upfield (δ = 6.763 ppm) and the downfield (δ = 6.673 ppm) resonances appear as a doublet (J = 1.5 Hz, resolved nearly to the baseline) and a broad singlet (with multiple shoulders), respectively. For Li 2 , the 1H resonance at δ = 7.231 ppm appears as a broadened triplet (a singlet with two shoulders).

32

In the presence of (-)-sparteine, yields of 15, as determined by 1H NMR spectra of crude mixtures, are in the 40-50% range.

34

The center part of the multiplet is somewhat broadened.