Download PDF
Synlett 2008(19): 3041-3045  
DOI: 10.1055/s-0028-1087345
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Sila-Sonogashira Cross-Coupling Reactions of Activated Aryl Chlorides with Alkynylsilanes

Yasushi Nishihara*, Eiji Inoue, Yoshiaki Okada, Kentaro Takagi
Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushimanaka, Okayama 700-8530, Japan
Fax: +81(86)2517855; e-Mail: ynishiha@cc.okayama-u.ac.jp;
Further Information

Publication History

Received 5 July 2008
Publication Date:
12 November 2008 (online)

    Permissions and Reprints All articles of this category

Abstract

The palladium/copper-cocatalyzed sila-Sonogashira cross-coupling reactions of activated aryl chlorides with alkynyl­silanes under strictly nonbasic conditions yield the unsymmetrical diarylethynes in moderate to good yields.

Key words

palladium - copper - Sonogashira reaction - alkynyl­silane - aryl chloride - diarylethynes

    References and Notes

  • 1a Nicolaou KC. Sorensen EJ. Classics in Total Synthesis   Wiley-VCH; Weinheim: 1996.  p.582-586  
    Google Scholar
  • 1b Brandsma L. Vasilevsky SF. Verkruijsse HD. Application of Transition Metal Catalysts in Organic Synthesis   Springer; Berlin: 1998.  p.179-225  
    Google Scholar
  • 1c Tour J. Acc. Chem. Res.  2000,  33:  791 
    Google Scholar
  • For examples of recent reviews, see:
  • 2a Sonogashira K. J. Organomet. Chem.  2002,  653:  46 
    Google Scholar
  • 2b Negishi E. Anastasia L. Chem. Rev.  2003,  103:  1979 
    Google Scholar
  • 2c Nicolaou KC. Bulger PG. Sarlah D. Angew. Chem. Int. Ed.  2005,  44:  4442 
    Google Scholar
  • 2d Yin L. Liebscher J. Chem. Rev.  2007,  107:  133 
    Google Scholar
  • 2e Chinchilla R. Nájera C. Chem. Rev.  2007,  107:  874 
    Google Scholar
  • 3a Ames DE. Bull D. Takundwa C. Synthesis  1981,  364 
    Google Scholar
  • 3b Menchi G. Scrivanti A. Matteoli U. J. Mol. Chem. A: Chem.  2000,  152:  77 
    Google Scholar
  • 4a Mori A. Shimada T. Kondo T. Sekiguchi A. Synlett  2001,  649 
    Google Scholar
  • 4b Mori A. Mohamed Ahmed MS. Sekiguchi A. Masui K. Koike T. Chem. Lett.  2002,  756 
    Google Scholar
  • 4c Mohamed Ahmed MS. Mori A. Tetrahedron  2004,  60:  9977 
    Google Scholar
  • 4d Mohamed Ahmed MS. Sekiguchi A. Masui K. Mori A. Bull. Chem. Soc. Jpn.  2005,  78:  160 
    Google Scholar
  • 5 Sonogashira K. Tohda Y. Hagihara N. Tetrahedron Lett.  1975,  4467 
    CrossrefGoogle Scholar
  • 6a Herrmann WA. Böhm VPW. Reisinger CP. J. Organomet. Chem.  1998,  576:  23 
    Google Scholar
  • 6b Alonso DA. Nájera C. Pacheco MC. Org. Lett.  2000,  2:  1283 
    Google Scholar
  • 6c Alonso DA. Najera C. Pacheco MC. Tetrahedron Lett.  2002,  43:  9365 
    Google Scholar
  • 6d Alonso DA. Najera C. Pacheco MC. Adv. Synth. Catal.  2003,  345:  1146 
    Google Scholar
  • 6e Alacid E. Alonso DA. Botella L. Nájera C. Pacheco MC. Chem. Rec.  2006,  6:  117 
    Google Scholar
  • 7a Bohm VPW. Herrmann WA. Eur. J. Org. Chem.  2000,  3679 
    Google Scholar
  • 7b Pal M. Parasuraman K. Gupta S. Yeleswarapu KR. Synlett  2002,  14:  1976 
    Google Scholar
  • 7c Fukuyama T. Shinmen M. Nishitani S. Sato M. Ryu I. Org. Lett.  2002,  4:  1691 
    Google Scholar
  • 7d Uozumi Y. Kobayashi Y. Heterocycles  2003,  59:  71 
    Google Scholar
  • 7e Urgaonkar S. Verkade JG. J. Org. Chem.  2004,  69:  5752 
    Google Scholar
  • 7f Heuzé K. Méry D. Gauss D. Blais J.-C. Astruc D. Chem. Eur. J.  2004,  10:  3936 
    Google Scholar
  • 7g Liang B. Dai M. Chen J. Yang Z. J. Org. Chem.  2005,  70:  391 
    Google Scholar
  • 7h Liang B. Huang M. You Z. Xiong Z. Lu K. Fathi R. Chen J. Yang Z. J. Org. Chem.  2005,  70:  6097 
    Google Scholar
  • 7i Cwik A. Hell Z. Figueras F. Tetrahedron Lett.  2006,  47:  3023 
    Google Scholar
  • 7j Kawanami H. Matsushima K. Sato M. Ikushima Y. Angew. Chem. Int. Ed.  2007,  46:  5129 
    Google Scholar
  • 7k Shi S. Zhang Y. Synlett  2007,  1843 
    Google Scholar
  • 7l Ljungdahl T. Bennur T. Dallas A. Emtenaes H. Maartensson J. Organometallics  2008,  27:  2490 
    Google Scholar
  • 8a Mori A. Kawashima J. Shimada T. Suguro M. Hirabayshi K. Nishihara Y. Org. Lett.  2000,  2:  2935 
    Google Scholar
  • 8b Kobayashi K. Sugie A. Takahashi M. Masui K. Mori A. Org. Lett.  2005,  7:  5083 
    Google Scholar
  • 9 Siemsen P. Livingston RC. Diederich F. Angew. Chem. Int. Ed.  2000,  39:  2632 
    Google Scholar
  • 10a Hundertmark T. Littke AF. Buchwald SL. Fu GC. Org. Lett.  2000,  2:  1729 
    Google Scholar
  • 10b Böhm VPW. Herrmann WA. Eur. J. Org. Chem.  2000,  3679 
    Google Scholar
  • 10c Alami M. Crousse B. Ferri F. J. Organomet. Chem.  2001,  624:  114 
    Google Scholar
  • 10d Soheili A. Albaneze-Walker J. Murry JA. Dormer PG. Hughes DL. Org. Lett.  2003,  5:  4191 
    Google Scholar
  • 11a Littke AF. Fu GC. Angew. Chem. Int. Ed.  2002,  41:  4176 ; and references therein
    Google Scholar
  • 11b Eberhard MR. Wang Z. Jensen CM. Chem. Commun.  2002,  818 
    Google Scholar
  • 11c Choudary BM. Madhi S. Chowdari NS. Kantam ML. Sreedhar B. J. Am. Chem. Soc.  2002,  124:  14127 
    Google Scholar
  • 11d Novak Z. Szabo A. Repasi J. Kotschy A. J. Org. Chem.  2003,  68:  3327 
    Google Scholar
  • 11e Faller JW. Kultyshev RG. Parr J. Tetrahedron Lett.  2003,  44:  451 
    Google Scholar
  • 11f Méry D. Heuzé K. Astruc D. Chem. Commun.  2003,  1934 
    Google Scholar
  • 11g Hillerich J. Plenio H. Chem. Commun.  2003,  3024 
    Google Scholar
  • 11h Soheili A. Albaneze-Walker J. Murry JA. Dormer PG. Hughes DL. Org. Lett.  2003,  5:  4191 
    Google Scholar
  • 11i Remmele H. Köllhofer A. Plenio H. Organometallics  2003,  22:  4098 
    Google Scholar
  • 11j Köllhofer A. Plenio H. Chem. Eur. J.  2003,  9:  1416 
    Google Scholar
  • 11k Heuzé K. Méry D. Gauss D. Astruc D. Chem. Commun.  2003,  2274 
    Google Scholar
  • 11l Hierso J.-C. Fihri A. Amardeil R. Meunier P. Doucet H. Santelli M. Ivanov V. Org. Lett.  2004,  6:  3473 
    Google Scholar
  • 11m Dubbaka SR. Vogel P. Adv. Synth. Catal.  2004,  346:  1793 
    Google Scholar
  • 11n Devashner RB. Moore LR. Shaughnessy KH. J. Org. Chem.  2004,  69:  7919 
    Google Scholar
  • 11o Kim JT. Gevorgyan V. J. Org. Chem.  2004,  69:  5638 
    Google Scholar
  • 11p Heuzé K. Méry D. Gauss D. Blais J.-C. Astruc D. Chem. Eur. J.  2004,  10:  3936 
    Google Scholar
  • 11q Anderson KW. Buchwald SL. Angew. Chem. Int. Ed.  2005,  44:  6173 
    Google Scholar
  • 11r Lemhadri M. Doucet H. Santelli M. Tetrahedron  2005,  61:  9839 
    Google Scholar
  • 11s Köllhofer A. Plenio H. Adv. Synth. Catal.  2005,  347:  1295 
    Google Scholar
  • 11t Cox RJ. Ritson DJ. Dane TA. Berge J. Charmant JPH. Kantacha A. Chem. Commun.  2005,  1037 
    Google Scholar
  • 11u Liang Y. Xie Y.-X. Li J.-H. J. Org. Chem.  2006,  71:  379 
    Google Scholar
  • 11v Yi C. Hua R. J. Org. Chem.  2006,  71:  2535 
    Google Scholar
  • 11w Ljungdahl T. Pettersson K. Albinsson B. Martensson J. J. Org. Chem.  2006,  71:  1677 
    Google Scholar
  • 11x Thathagar MB. Rothenberg G. Org. Biomol. Chem.  2006,  4:  111 
    Google Scholar
  • 11y Cwik A. Hell Z. Figueras F. Tetrahedron Lett.  2006,  47:  3023 
    Google Scholar
  • 11z Fleckenstein CA. Plenio H. Organometallics  2007,  26:  2758 
    Google Scholar
  • 12a Doucet H. Hierso J.-C. Angew. Chem. Int. Ed.  2007,  46:  834 
    Google Scholar
  • 12b Yi C. Hua R. Zeng H. Huanga Q. Adv. Synth. Catal.  2007,  349:  1738 
    Google Scholar
  • 12c Likhar PR. Subhas MS. Roy M. Roy S. Kantam ML. Helv. Chim. Acta  2008,  91:  259 
    Google Scholar
  • 13 Adjabeng G. Brenstrum T. Frampton CS. Robertson AJ. Hillhouse J. McNulty J. Capretta A. J. Org. Chem.  2004,  69:  5082 
    CrossrefPubMedGoogle Scholar
  • 14 Feuerstein M. Doucet H. Santelli M. Tetrahedron Lett.  2004,  45:  8443 
    CrossrefGoogle Scholar
  • 15 Liang Y. Xie Y.-X. Li J.-H. J. Org. Chem.  2006,  71:  379 
    CrossrefPubMedGoogle Scholar
  • 16 Juo Y. Gao H. Li Y. Huang W. Lu W. Zhang Z. Tetrahedron  2006,  62:  2465 
    CrossrefGoogle Scholar
  • 17 Köllhofer A. Pullmann T. Plenio H. Angew. Chem. Int. Ed.  2003,  42:  1056 
    CrossrefPubMedGoogle Scholar
  • 18 Eberhard MR. Wang Z. Jensen CM. Chem. Commun.  2002,  818 
    CrossrefGoogle Scholar
  • 19a Nishihara Y. Ikegashira K. Mori A. Hiyama T. Chem. Lett.  1997,  1233 
    Google Scholar
  • 19b Nishihara Y. Ikegashira K. Hirabayashi K. Ando J. Mori A. Hiyama T. J. Org. Chem.  2000,  65:  1780 
    Google Scholar
  • The copper-free version of sila-Sonogashira cross-coupling reaction has been achieved using a palladium/imidazolium salt system, see:
  • 20a Yang C. Nolan SP. Organometallics  2002,  21:  1020 
    Google Scholar
  • 20b Hillier AC. Grasa GA. Viciu MS. Lee HM. Yang C. Nolan SP. J. Organomet. Chem.  2002,  653:  69 
    Google Scholar
  • For examples of modified sila-Sonogashira cross-coupling reaction under basic conditions, see:
  • 21a Mio MJ. Kopel LC. Braun JB. Gadzikwa TL. Hull KL. Brisbois RG. Markworth CJ. Grieco PA. Org. Lett.  2002,  4:  3199 
    Google Scholar
  • 21b Gil-Moltóa J. Nájera C. Adv. Synth. Catal.  2006,  348:  1874 
    Google Scholar
  • 22 Sørensen US. Pombo-Villar E. Tetrahedron  2005,  61:  2697 
    CrossrefGoogle Scholar
  • 23 Nishihara Y. Inoue Y. Fujisawa M. Takagi K. Synlett  2005,  2309 
    Article in Thieme ConnectGoogle Scholar
  • 24 The presence of the copper(I) cocatalyst inhibited product formation, see: Gelman D. Buchwald SL. Angew. Chem. Int. Ed.  2003,  42:  5993 
    CrossrefPubMedGoogle Scholar
  • 25a Hatanaka Y. Hiyama T. J. Org. Chem.  1988,  53:  918 
    Google Scholar
  • 25b Hatanaka Y. Hiyama T. Synlett  1991,  845 
    Google Scholar
  • 26 Nishihara Y. Takemura M. Mori A. Osakada K. J. Organomet. Chem.  2001,  620:  282 
    CrossrefGoogle Scholar
27

Typical Procedure for the Sila-Sonogashira Cross-Coupling Reactions of Aryl Chlorides 2 with Alkynylsilanes 1
To a solution of Pd(OAc)2 (45 mg, 0.2 mmol, 10 mol%) and (-)-DIOP (100 mg, 0.2 mmol, 10 mol%) in dry DMF (8 mL) were added 1-(4-methoxypheny)-2-trimethylsilylethyne (1b, 519 µL, 2.4 mmol), 4-cyanophenyl chloride (2b, 275 mg, 2 mmol), and CuCl (20 mg, 0.2 mmol, 10 mol%) at r.t. The dark red suspension was heated for 12 h at 120 ˚C and monitored by GC and TLC. After completion of the reaction, the reaction mixture was quenched with 1 M HCl and extracted with Et2O (3 × 20 mL). The combined organics were washed with brine and dried over anhydrous MgSO4. Filtration and concentration with a rotary evaporator gave a viscous oil. The residue was purified by flash column chromatography on SiO2 (hexane-Et2O, 8:2, R f  = 0.39), 3h (331 mg, 1.42 mmol, 71%) was obtained as a white solid. ¹H NMR (300 MHz, CDCl3): δ = 3.84 (s, 3 H), 6.89-6.92 (m,
2 H), 7.47-7.50 (m, 2 H), 7.56-7.64 (m, 4 H).