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Synlett 2011(2): 280-284  
DOI: 10.1055/s-0030-1259087
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

The Cobalt-Way to Heterophenylenes: Syntheses of 2-Thianorbiphenylenes, Monoazabiphenylenes, and Linear 1-Aza[3]phenylene {Biphenyleno[2,3-a]cyclobuta[1,2-b]pyridine}

Verena Engelhardta, J. Gabriel Garciaa, Aude A. Hubauda, Konstantin A. Lyssenkob, Spyros Spyroudisa, Tatiana V. Timofeevab, Paul Tongwab, K. Peter C. Vollhardt*a
a Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460, USA
Fax: +1(510)6435208; e-Mail: kpcv@berkeley.edu;
b Department of Natural Sciences, New Mexico Highlands University, Las Vegas, NM 87701, USA
Further Information

Publication History

Received 19 October 2010
Publication Date:
07 December 2010 (online)

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Abstract

CpCo(CO)2 catalyzes the cocyclization of ortho-diethynylthiophenes and -pyridines with alkynes to construct the corresponding thia- and azaphenylenes. This strategy is applied to the synthesis of linear 1-aza[3]phenylene, the first higher heterophenylene.

Key words

alkynes - cobalt - cyclization - heterocycles - transition metals

    References and Notes

  • For a review, see:
  • 1a Miljanić OŠ. Vollhardt KPC. In Carbon-Rich Compounds: From Molecules to Materials   Haley MM. Tykwinski RR. Wiley-VCH; Weinheim: 2006.  p.140 
    Google Scholar
  • See also:
  • 1b Mohler DL. Kumaraswamy S. Stanger A. Vollhardt KPC. Synlett  2006,  2981 
    Google Scholar
  • For selected references and patents, see:
  • 2a Nakatsuka M. inventors; JP 2010219301 A  20100930.  ; Chem. Abstr. 2010, 153, 446064
    Google Scholar
  • 2b Kano T, Suzuki K, and Nakada S. inventors; JP 2010146833 A  20100701.  ; Chem. Abstr. 2010, 153, 130239
    Google Scholar
  • 2c Schmälzlin E, Eich S, Dosche C, and Löhmannsröben H.-G. inventors; DE 102008044317 A1  20100617.  ; Chem. Abstr. 2010, 153, 52277
    Google Scholar
  • 2d Schmälzlin E, Eich S, Dosche C, and Löhmannsröben H.-G. inventors; WO 2010063806 A1  20100610.  ; Chem. Abstr. 2010, 153, 52265
    Google Scholar
  • 2e Watanabe M, and Ohashi T. inventors; JP 2010070473 A  20100402.  ; Chem. Abstr. 2010, 152, 405420
    Google Scholar
  • 2f Thalacker C, Hailand B, Dede K, and Eckert AS. inventors; WO 2009152211 A2  20091217.  ; Chem. Abstr. 2009, 152, 76163
    Google Scholar
  • 2g Watanabe M, and Ohashi T. inventors; JP 2008247853 A  20081016.  ; Chem. Abstr. 2008, 149, 471208
    Google Scholar
  • 2h Watanabe M. Ohashi T. Yamamoto T. TOSOH Res. Technol. Rev.  2007,  51:  21 
    Google Scholar
  • 2i Dosche C. Mickler W. Löhmannsröben H.-G. Agenet N. Vollhardt KPC.
    J. Photochem. Photobiol., A  2007,  188:  371 
    Google Scholar
  • 2j Taillemite S. Aubert C. Fichou D. Malacria M. Tetrahedron Lett.  2005,  46:  8325 
    Google Scholar
  • 3 Albright TA. Dosa PI. Grossmann TN. Khrustalev VN. Oloba OA. Padilla R. Paubelle R. Stanger A. Timofeeva TV. Vollhardt KPC. Angew. Chem. Int. Ed.  2009,  48:  9853 
    CrossrefGoogle Scholar
  • For very recent reviews, see:
  • 4a Mishra A. Ma C.-Q. Bäuerle P. Chem. Rev.  2009,  109:  1141 
    Google Scholar
  • 4b Pron A. Gawrys P. Zagorska M. Djurado D. Demadrille R. Chem. Soc. Rev.  2010,  39:  2577 
    Google Scholar
  • For selected very recent advances in the topologically relevant heteroacenes, see:
  • 5a Bunz UHF. Pure Appl. Chem.  2010,  82:  953 
    Google Scholar
  • 5b Santato C. Favaretto L. Melucci M. Zanelli A. Gazzano M. Monari M. Isik D. Banville D. Bertolazzi S. Loranger S. Cicoira F. J. Mater. Chem.  2010,  20:  669 
    Google Scholar
  • 5c Tang Q. Liang Z. Liu J. Xu J. Miao Q. Chem. Commun.  2010,  46:  2977 
    Google Scholar
  • 5d Skabara PJ. In Handbook of Thiophene-Based Materials   Vol. 1:  Perepichka IF. Perepichka DF. Wiley; Chichester: 2009.  p.219 
    Google Scholar
  • 5e Tang ML. Mannsfeld CB. Sun Y.-S. Becerril HA. Bao Z. J. Am. Chem. Soc.  2009,  131:  882 
    Google Scholar
  • 5f Gao P. Beckmann D. Tsao HN. Feng X. Enkelmann V. Baumgarten M. Pisula W. Müllen K. Adv. Mater.  2009,  21:  213 
    Google Scholar
  • 6 Shepherd MK. Cyclobutarenes. The Chemistry of Benzocyclobutene, Biphenylene, and Related Compounds   Elsevier; Amsterdam: 1991. 
    Google Scholar
  • 7 Sugihara Y. Yagi T. Murata I. Imamura A. J. Am. Chem. Soc.  1992,  114:  1479 
    CrossrefGoogle Scholar
  • 9 Berris BC. Hovakeemian GH. Lai Y.-H. Mestdagh H. Vollhardt KPC. J. Am. Chem. Soc.  1985,  107:  5670 
    CrossrefGoogle Scholar
  • 10 Garcia JG. Liu Y.-H. Fronczek FR. J. Chem. Crystallogr.  1996,  26:  607 
    CrossrefGoogle Scholar
  • 11 Angelici RJ. Organometallics  2001,  20:  1259 
    CrossrefGoogle Scholar
  • 12 Garratt PJ. Vollhardt KPC. J. Am. Chem. Soc.  1972,  94:  7087 
    CrossrefGoogle Scholar
  • 13 Takayama Y. Hanazawa T. Andou T. Muraoka K. Ohtani H. Takahashi M. Sato F. Org. Lett.  2004,  6:  4253 
    CrossrefGoogle Scholar
  • 14 Barton JW. Walker RB. Tetrahedron Lett.  1975,  16:  569 
    CrossrefGoogle Scholar
  • 15 Kim C.-S. Russell KC. J. Org. Chem.  1998,  63:  8229 
    CrossrefGoogle Scholar
  • 16 Chen TK. Flowers WT. J. Chem. Soc., Chem. Commun.  1980,  1139 
    Google Scholar
  • 17 Perthuisot C. Edelbach BL. Zubris DL. Simhai N. Iverson CN. Müller C. Satoh T. Jones WD. J. Mol. Catal. A  2002,  189:  157 
    Google Scholar
  • See:
  • 18a Garcia Y. Schoenebeck F. Legault CY. Merlic CA. Houk KN. J. Am. Chem. Soc.  2009,  131:  6632 
    Google Scholar
  • 18b Wang J.-R. Manabe K. Synthesis  2009,  1405 
    Google Scholar
  • 18c Fairlamb IJS. Chem. Soc. Rev.  2007,  36:  1036 
    Google Scholar
  • 19 Kumaraswamy S. Jalisatgi SS. Matzger AJ. Miljanić OŠ. Vollhardt KPC. Angew. Chem. Int. Ed.  2004,  43:  3711 
    CrossrefGoogle Scholar
  • 20 Rubin Y. Lin SS. Knobler CB. Anthony J. Boldi AM. Diederich F. J. Am. Chem. Soc.  1991,  113:  6943 
    CrossrefGoogle Scholar
  • See:
  • 21a Gibson KJ. d’Alarcao M. Leonard NJ. J. Org. Chem.  1985,  50:  2462 
    Google Scholar
  • 21b Hull R. MacBride JAH. Wright PM. J. Chem. Res., Synop.  1984,  328 ; J. Chem. Res., Miniprint 1984, 3001
    Google Scholar
  • There are only two X-ray crystallographic structure determinations of azabiphenylene derivatives.
  • 22a 1,8-Diazabiphenylene: Deroski BR. Ricci JS. MacBride JAH. Markgraf JH. Can. J. Chem.  1984,  62:  2235 
    Google Scholar
  • 22b N-Allyl-2,7-diazabiphenylenium bromide: Kanoktanaporn S. MacBride JAH. King TJ. J. Chem. Res., Synop.  1980,  204 ; J. Chem. Res., Miniprint 1980, 2911
    Google Scholar
  • 23 Pyckhout W. Horemans N. Van Alsenoy C. Geise HJ. Rankin DWH. J. Mol. Struct.  1987,  156:  315 
    CrossrefGoogle Scholar
  • 24 Fawcett JK. Trotter J. Acta Crystallogr.  1966,  20:  87 
    CrossrefGoogle Scholar
  • 25 Frank NL. Siegel JS. In Advances in Theoretically Interesting Molecules   Vol. 3:  Thummel RP. JAI; London: 1995.  p.209 
    Google Scholar
  • 26 Defined as the sum of the deviation of all bond distances from the average: Maksić ZB. Kovaček D. Eckert-Maksić M. Böckmann M. Klessinger M. J. Phys. Chem.  1995,  99:  6410 
    CrossrefGoogle Scholar
  • 27 Desiraju GR. Gavezzotti A. J. Chem. Soc., Chem. Commun.  1989,  621 
    Google Scholar
  • 28 Schleifenbaum A. Feeder N. Vollhardt KPC. Tetrahedron Lett.  2001,  42:  7329 
    CrossrefGoogle Scholar
8

The structures of all new compounds (Scifinder) were in accord with their analytical and/or spectroscopic properties; see Supporting Information. CCDC 797197 and CCDC 797198 contain the supplementary crystallographic data for 12 and 14, respectively. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Selected Data Compound 3a: colorless crystals; mp 80-81 ˚C (EtOH-H2O). IR (hexanes): 3010, 1364, 1250, 1064, 1031, 854 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 7.18 (s, 2 H), 6.53 (s, 2 H), 0.32 (s, 18 H). ¹³C NMR (75 MHz, CDCl3): δ = 148.2, 147.7, 144.8, 124.1, 113.2, 2.63. MS (EI, 70 eV): m/z (%) = 302 (100) [M]+, 273 (12), 272 (22), 271 (85), 215 (13), 73 (58). UV/Vis (EtOH): λmax (log ε) = 257 sh (5.04), 262 (5.16), 337 (4.37), 353 (4.43) nm. Anal. Calcd for C16H22SSi2: C, 63.51; H, 7.33. Found: C, 63.84; H, 7.58.
Compound 5: opaque oil. ¹H NMR (400 MHz, CDCl3): δ = 8.12 (d, J = 5 Hz, 1 H), 7.60 (br s, 1 H), 7.32 (s, 1 H), 7.27 (s, 1 H), 6.38 (d, J = 5 Hz, 1 H), 0.30 (s, 18 H). MS (EI, 70 eV): m/z (%) = 297 (100) [M]+, 282 (70), 266 (20), 239 (12), 73 (53). HRMS (EI): m/z [M]+ calcd for C17H23NSi2: 297.1369; found: 297.1361. UV/Vis (hexane): λmax (log ε) = 231 (3.56), 301 (3.02), 325 (3.25), 340 (3.31) nm.
Compound 7: opaque oil. ¹H NMR (500 MHz, CDCl3; assignments by 2D NMR): δ = 7.64 (d, J = 5.5 Hz, 1 H, H²), 7.26 (s, 1 H, H8), 7.16 (s, 1 H, H5), 6.74 (d, J = 6.5 Hz, 1 H, H4), 6.51 (dd, J = 6.25, 6.25 Hz, 1 H, H³), 0.34 (s, 9 H, Me3Si), 0.33 (s, 9 H, Me3Si). ¹³C NMR (100 MHz, CDCl3): δ = 173.1 (C8b), 152.7 (C8a), 150.9 (C6/7), 150.5 (C4b), 150.2 (C4a), 149.3 (C6/7), 145.7 (C²), 124.6 (C5), 124.3 (C8), 122.4 (C³), 122.0 (C4), 2.00 (SiCH3), 1.99 (SiCH3). MS (EI, 70 eV): m/z (%) = 297 (100) [M]+, 282 (72), 266 (32), 239 (17), 73 (55). HRMS (EI): m/z [M]+ calcd for C17H23NSi2: 297.1369; found: 297.1361. UV/Vis (hexane): λmax (log ε) = 241 (4.01), 270 (3.76), 347 (3.50), 362 nm (3.40).
Compound 14: deep red crystals; mp 225-226 ˚C (dec.; hexane). IR (neat): 3069, 2929, 2855, 1643, 1585, 1415, 1349, 1246, 1186, 1153, 865, 733 cm-¹. ¹H NMR (400 MHz, CDCl3; assignments by 2D NMR): δ = 7.48 (dd, J = 6.0, 1.2 Hz, 1 H, H²), 6.72 (m, 2 H, H7,8), 6.53 (m, 2 H, H6,9), 6.48 (d, J = 1.2 Hz, 1 H, H¹0), 6.45 (dd, J = 6.8, 1.2 Hz, 1 H, H4), 6.40 (s, 1 H, H5), 6.39 (dd, J = 6.4, 6.4 Hz, 1 H, H³). ¹³C NMR (150 MHz, CD2Cl2): δ = 172.2 (C¹0b), 155.4 (C4b/¹0a), 155.0 (C4b/¹0a), 153.9 (C5a/9b), 153.6 (C5a/9b), 150.4 (C5b/9a), 150.1 (C5b/9a), 148.9 (C4a), 145.2 (C²), 129.2 (C7/8), 129.0 (C7/8), 122.3 (C³), 119.2 (C4), 117.1 (C6/9), 117.0 (C6/9), 112.2 (C5), 111.4 (C¹0). MS (EI, 70 eV): m/z (%) = 227 (100) [M]+, 201 (30), 174 (7), 150 (4), 123 (3), 113 (14), 100 (22). HRMS (EI): m/z [M]+ calcd for C17H9N: 227.0735; found: 227.0739. UV/Vis (hexane): λmax (log ε) = 266 (5.48), 275 (5.60), 299 (4.97), 311 (4.91), 387 sh (4.68), 407 (5.07), 421 sh (5.02), 433 (5.28) nm.