Download PDF
Synlett 2009(19): 3147-3150  
DOI: 10.1055/s-0029-1218341
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Palladium-Catalyzed Double Cross-Coupling Reaction of vic-Diborylalkenes and -arenes with vic-Bromo(bromomethyl)arenes

Masaki Shimizu*, Yosuke Tomioka, Ikuhiro Nagao, Tamejiro Hiyama
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto University Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
Fax: +81(75)3832445; e-Mail: m.shimizu@hs2.ecs.kyoto-u.ac.jp;
Further Information

Publication History

Received 19 September 2009
Publication Date:
03 November 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

Efficient annulation of vic-diborylalkenes and -arenes with vic-bromo(bromomethyl)arenes has been achieved, using Pd(PPh3)4 as a catalyst in the presence of Cs2CO3 and water in THF at 60 ˚C, giving rise to the corresponding indene and fluorene derivatives in good to high yields.

Key words

annulations - arenes - boron - bromine - cross-coupling

    References and Notes

  • 1a Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998. 
    Google Scholar
  • 1b Cross-Coupling Reaction: A Practical Guide   Miyaura N. Springer; Berlin: 2002. 
    Google Scholar
  • 1c Metal-Catalyzed Cross-Coupling Reactions   de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • 1d Hassan J. Sevignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 
    Google Scholar
  • 1e Negishi E.-i. Bull. Chem. Soc. Jpn.  2007,  80:  233 
    Google Scholar
  • 1f Knochel P. Betzemeier B. Transmetalation Reactions Producing Organocopper Reagents, In Modern Organocopper Chemistry   Krause N. Wiley-VCH; Weinheim: 2002.  p.45-78  
    Google Scholar
  • 1g Evano G. Blanchard N. Toumi M. Chem. Rev.  2008,  108:  3054 
    Google Scholar
  • 1h Iyoda M.
    Adv. Synth. Catal.  2009,  351:  984 
    Google Scholar
  • 2a Takahashi T. Hara R. Nishihara Y. Kotora M. J. Am. Chem. Soc.  1996,  118:  5154 
    Google Scholar
  • 2b Yamamoto Y. Ohno T. Itoh K. Chem. Commun.  1999,  1543 
    Google Scholar
  • 2c Takahashi T. Sun WH. Duan Z. Shen B. Org. Lett.  2000,  2:  1197 
    Google Scholar
  • 2d Takahashi T. Li Y. Stepnicka P. Kitamura M. Liu Y. Nakajima K. Kotora M. J. Am. Chem. Soc.  2002,  124:  576 
    Google Scholar
  • 2e Yamamoto Y. Ohno T. Itoh K. Chem. Eur. J.  2002,  8:  4734 
    Google Scholar
  • 2f Zhou X. Li Z. Wang H. Kitamura M. Kanno KI. Nakajima K. Takahashi T. J. Org. Chem.  2004,  69:  4559 
    Google Scholar
  • 2g Hilton CL. Jamison CR. King BT. J. Am. Chem. Soc.  2006,  128:  14824 
    Google Scholar
  • 2h Hilton CL. Jamison CR. Zane HK. King BT. J. Org. Chem.  2009,  74:  405 
    Google Scholar
  • 2i Zhou L. Nakajima K. Kanno K.-i. Takahashi T. Tetrahedron Lett.  2009,  50:  2722 
    Google Scholar
  • 3a Xue X. Scott LT. Org. Lett.  2007,  9:  3937 
    Google Scholar
  • 3b Shimizu M. Nagao I. Tomioka Y. Hiyama T. Angew. Chem. Int. Ed.  2008,  47:  8096 
    Google Scholar
  • 3c Goodby JW. Hird M. Toyne KJ. Watson T. J. Chem. Soc., Chem. Commun.  1994,  1701 
    Google Scholar
  • 3d Nagao I. Shimizu M. Hiyama T. Angew. Chem. Int. Ed.  2009,  48:  7573 
    Google Scholar
  • Recent examples of transition-metal-catalyzed annulative synthesis of indene and fluorene derivatives:
  • 4a Park EJ. Kim SH. Chang S. J. Am. Chem. Soc.  2008,  130:  17268 
    Google Scholar
  • 4b Miyamoto M. Harada Y. Tobisu M. Chatani N. Org. Lett.  2008,  10:  2975 
    Google Scholar
  • 4c Zhang D. Liu Z. Yum EK. Larock RC. J. Org. Chem.  2007,  72:  251 
    Google Scholar
  • 4d Dong C.-G. Yeung P. Hu Q.-S. Org. Lett.  2007,  9:  363 
    Google Scholar
  • 4e Kuninobu Y. Nishina Y. Shouho M. Takai K. Angew. Chem. Int. Ed.  2006,  45:  2766 
    Google Scholar
  • 4f Dong C.-G. Hu Q.-S. Angew. Chem. Int. Ed.  2006,  45:  2289 
    Google Scholar
  • 4g Kuninobu Y. Kawata A. Takai K. J. Am. Chem. Soc.  2005,  127:  13498 
    Google Scholar
  • 4h Chang KJ. Rayabarapu DK. Cheng CH.
    J. Org. Chem.  2004,  69:  4781 
    Google Scholar
  • 4i Lautens M. Marquardt T. J. Org. Chem.  2004,  69:  4607 
    Google Scholar
  • 4j Xi Z. Guo R. Mito S. Yan H. Kanno KI. Nakajima K. Takahashi T. J. Org. Chem.  2003,  68:  1252 
    Google Scholar
  • 5a Huffman JW. Padgett LW. Curr. Med. Chem.  2005,  12:  1395 
    Google Scholar
  • 5b Scherf U. Neher D. Polyfluorene   Springer; Berlin: 2008. 
    Google Scholar
  • vic-Diborylalkenes were prepared by Pt-catalyzed 1,2-diborylation of alkynes with bis(pinacolato)diboron. See:
  • 6a Ishiyama T. Matsuda N. Miyaura N. Suzuki A.
    J. Am. Chem. Soc.  1993,  115:  11018 
    Google Scholar
  • 6b Ishiyama T. Matsuda N. Murata M. Ozawa F. Suzuki A. Miyaura N. Organometallics  1996,  15:  713 
    Google Scholar
  • 9a Langle S. Abarbri M. Duchêne A. Tetrahedron Lett.  2003,  44:  9255 
    Google Scholar
  • Reviews on Pd-catalyzed reactions of benzylic derivatives:
  • 9b Liegault B. Renaud J.-L. Bruneau C. Chem. Soc. Rev.  2008,  37:  290 
    Google Scholar
  • 9c Kuwano R. Synthesis  2009,  1049 
    Google Scholar
  • vic-Diborylbenzene 1d was prepared from 1,2-dibromo-benzene with pinacolborane using the Buchwald’s protocol for Pd-catalyzed borylation of bromoarenes:
  • 11a Billingsley KL. Buchwald SL. J. Org. Chem.  2008,  73:  5589 
    Google Scholar
  • Stepwise coupling reactions of diborylbenzenes with two aryl halides leading to terphenyls were reported:
  • 11b Noguchi H. Shioda T. Chou CM. Suginome M. Org. Lett.  2008,  10:  377 
    Google Scholar
  • 11c Shimizu M. Shimono K. Kurahashi T. Kiyomoto S.-i. Nagao I. Hiyama T. Bull. Chem. Soc. Jpn.  2008,  81:  518 
    Google Scholar
7

For details, see Supporting Information.

8

Crystallographic Data for 4a
C27H28BBrO2, M = 475.21, triclinic, a = 9.9742(7), b = 10.2322(7), c = 13.9705(9) Å, α = 86.0320(10), β = 69.5850(10), γ = 64.4340(10)˚, U = 1199.82(14)
ų, T = 300 K, space group P1, Z = 2, 6571 reflections collected, unique 4380 (R int = 0.0142), final R indices [I > 2σ(I)] R1 = 0.0558, wR2 = 0.1530. CCDC-737101 contains the supplementary crystallographic data.

10

In some cases, slight modification of a base was necessary for attaining a good yield of the product. On the other hand, the reaction of 1-bromo-2-(1-bromoethyl)benzene with 1a failed so far although various bases and conditions were screened.