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Synlett 2008(16): 2508-2512  
DOI: 10.1055/s-2008-1078051
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Aryl Norbornanes and Analogues via Palladium-Catalyzed Hydroarylation with Arenediazonium Tetrafluoroborates

Gabriele Bartoli, Sandro Cacchi*, Giancarlo Fabrizi, Antonella Goggiamani
Dipartimento di Chimica e Tecnologie del Farmaco, Università degli Studi ‘La Sapienza’, P. le A. Moro 5, 00185 Rome, Italy
Fax: +39(06)49912780; e-Mail: sandro.cacchi@uniroma1.it;
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Publikationsverlauf

Received 18 June 2008
Publikationsdatum:
12. September 2008 (online)

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Abstract

The palladium-catalyzed hydroarylation of arenediazonium tetrafluoroborates with norbornene derivatives and analogues in the presence of Pd(OAc)2 and i-Pr3SiH in THF affords hydroarylation products containing the added aryl unit in the exo position in good to high yields. The reaction tolerates a variety of useful functional groups and can be performed as a one-pot procedure generating the arenediazonium salt in situ.

Key words

norbornene - palladium - hydroarylation - arenediazonium salts

    References and Notes

  • 1 For an excellent recent review on the palladium-chemistry of arenediazonium salts, see: Roglans A. Pla-Quintana A. Moreno-Mañas M. Chem. Rev.  2006,  106:  4622 
    CrossrefPubMedSuche in Google Scholar
  • For some recent selected references, see:
  • 2a Ma Y. Song C. Chai Q. Ma C. Andrus MB. Synthesis  2003,  2886 
  • 2b Wang C. Tan L.-S. He J.-P. Hu H.-W. Xu J.-H. Synth. Commun.  2003,  33:  773 
    Suche in Google Scholar
  • 2c Masllorens J. Moreno-Manãs M. Pla-Quintana A. Roglans A. Org. Lett.  2003,  5:  1559 
    Suche in Google Scholar
  • 2d Schmidt B. Chem. Commun.  2003,  1656 
  • 2e Nelson ML. Ismail MY. McIntyre L. Bhatia B. Viski P. Hawkins P. Rennie G. Andorsky D. Messersmith D. Stapleton K. Dumornay J. Sheahan P. Verma AK. Warchol T. Levy SB. J. Org. Chem.  2003,  68:  5838 
    Suche in Google Scholar
  • 2f Dai M. Liang B. Wang C. Chen J. Yang Z. Org. Lett.  2004,  6:  221 
    Suche in Google Scholar
  • 2g Kabalka GW. Dong G. Venkataiah B. Tetrahedron Lett.  2004,  45:  2775 
    Suche in Google Scholar
  • 2h Xu L.-H. Zhang Y.-Y. Wang X.-L. Chou J.-Y. Dyes Pigm.  2004,  62:  283 
    Suche in Google Scholar
  • 2i Sabino AA. Machado AHL. Correia CRD. Eberlin MN. Angew. Chem. Int. Ed.  2004,  43:  2514 
    Suche in Google Scholar
  • 2j Sabino AA. Machado AHL. Correia CRD. Eberlin MN. Angew. Chem. Int. Ed.  2004,  43:  2514 ; corrigendum: Angew. Chem. Int. Ed. 2004, 43, 4389
    Suche in Google Scholar
  • 2k Masllorens J. Bouquillon S. Roglans A. Hénin F. Muzart J. J. Organomet. Chem.  2005,  690:  3822 
    Suche in Google Scholar
  • 2l Garcia ALL. Carpes MJS. Montes de Oca ACB. dos Santos MAG. Santana CC. Correia CRD. J. Org. Chem.  2005,  70:  1050 
    Suche in Google Scholar
  • 2m Artuso E. Barbero M. Degani I. Dughera S. Fochi R. Tetrahedron  2006,  62:  3146 
    Suche in Google Scholar
  • 2n Pastre JC. Correia CRD. Org. Lett.  2006,  8:  1657 
    Suche in Google Scholar
  • 2o Perez R. Veronese D. Coelho F. Antunes OAC. Tetrahedron Lett.  2006,  47:  1325 
    Suche in Google Scholar
  • For some recent references, see:
  • 3a Peyroux E. Berthiol F. Doucet H. Santelli M. Eur. J. Org. Chem.  2004,  1075 
  • 3b Jo J. Chi C. Höger S. Wegner G. Yoon DY. Chem. Eur. J.  2004,  10:  2681 
    Suche in Google Scholar
  • 3c See also: Gallo V. Mastrorilli P. Nobile CF. Paolillo R. Taccardi N. Eur. J. Inorg. Chem.  2005,  582 
  • 3d Darses S. Genet JP. Eur. J. Org. Chem.  2003,  4313 
  • 4a Kikukawa K. Kono K. Wada F. Matsuda T. Chem. Lett.  1982,  35 
  • 4b Kikukawa K. Kono K. Wada F. Matsuda T. J. Org. Chem.  1983,  48:  1333 
    Suche in Google Scholar
  • 4c Kikukawa K. Idemoto T. Katayama A. Kono K. Wada F. Matsuda T. J. Chem. Soc., Perkin Trans. 1  1987,  1511 
  • 4d Dughera S. Synthesis  2006,  1117 
  • 5a Kikukawa K. Kono K. Nagira K. Wada F. Matsuda T. Tetrahedron Lett.  1980,  21:  2877 
    Suche in Google Scholar
  • 5b Nagira K. Kikukawa K. Wada F. Matsuda T. J. Org. Chem.  1980,  45:  2365 
    Suche in Google Scholar
  • 5c Kikukawa K. Kono K. Nagira K. Wada F. Matsuda T. J. Org. Chem.  1981,  46:  4413 
    Suche in Google Scholar
  • 5d Sengupta S. Sadhukhan SK. Bhattacharyya S. Guha J. J. Chem. Soc., Perkin Trans. 1  1998,  407 
  • 5e Kikukawa K. Totoki T. Wada F. Matsuda T. J. Organomet. Chem.  1984,  270:  283 
    Suche in Google Scholar
  • 5f Siegrist U. Rapold T. Blaser H.-U. Org. Process Res. Dev.  2003,  7:  429 
    Suche in Google Scholar
  • 6 Pelzer G. Keim W. J. Mol. Catal. A: Chem.  1999,  139:  235 
    CrossrefSuche in Google Scholar
  • 7a Willis DM. Strongin RM. Tetrahedron Lett.  2000,  41:  8683 
    Suche in Google Scholar
  • 7b Ma Y. Song C. Jiang W. Xue G. Cannon JF. Wang X. Andrus MB. Org. Lett.  2003,  5:  4635 
    Suche in Google Scholar
  • 8 Cacchi S. Fabrizi G. Goggiamani A. Persiani D. Org. Lett.  2008,  10:  1597 
    CrossrefPubMedSuche in Google Scholar
  • 9a Arcadi A. Marinelli F. Bernocchi E. Cacchi S. Ortar G. J. Organomet. Chem.  1989,  368:  249 
    Suche in Google Scholar
  • 9b Larock RC. Johnson PL. Chem. Commun.  1989,  1368 
  • 10 Mayo P. Tam W. Tetrahedron  2002,  58:  9527 
    CrossrefSuche in Google Scholar
  • 11 Wållberg A. Magnusson G. Tetrahedron  2000,  56:  8533 
    CrossrefSuche in Google Scholar
  • 12a Clayton SC. Regan AC. Tetrahedron Lett.  1993,  34:  7493 
    Suche in Google Scholar
  • 12b Bai D. Xu R. Chu G. Zhu X. J. Org. Chem.  1996,  61:  4600 
    Suche in Google Scholar
  • 13a Kasyan A. Wagner C. Maier ME. Tetrahedron  1998,  54:  8047 
    Suche in Google Scholar
  • 13b Carroll FI. Brieaddy LE. Navarro HA. Damaj MI. Martin BR. J. Med. Chem.  2005,  48:  7491 
    Suche in Google Scholar
  • 14a Brunner H. Kramler K. Synthesis  1991,  1121 
  • 14b Sakuraba S. Awano K. Achiwa K. Synlett  1994,  291 
  • 14c Sakuraba S. Okada T. Morimoto T. Achiwa K. Chem. Pharm. Bull.  1995,  43:  927 
    Suche in Google Scholar
  • 14d Wu X.-Y. Xu H.-D. Zhoua Q.-L. Chan ASC. Tetrahedron: Asymmetry  2000,  11:  1255 
    Suche in Google Scholar
  • 14e Wu X.-Y. Xu H.-D. Tang F.-Y. Zhou Q.-L. Tetrahedron: Asymmetry  2001,  12:  2565 
    Suche in Google Scholar
  • 15a Kikukawa K. Nagira K. Wada F. Matsuda T. Tetrahedron  1981,  37:  31 
    Suche in Google Scholar
  • 15b Sengupta S. Bhattacharyya S. J. Chem. Soc., Perkin Trans. 1  1993,  1943 
  • 19 Doyle MP. Bryker WJ. J. Org. Chem.  1979,  44:  1572 
    CrossrefSuche in Google Scholar
  • 21a Hatanaka Y. Hiyama T. Tetrahedron Lett.  1990,  31:  2719 
    Suche in Google Scholar
  • 21b Hatanaka Y. Hiyama T. J. Am. Chem. Soc.  1990,  112:  7783 
    Suche in Google Scholar
16

When 1a was subjected to the reaction conditions reported in Table  [¹] (entry 5) omitting Pd(OAc)2 no reduction product 4 was formed suggesting that the reduction of 1a to 4 proceeds through a palladium-catalyzed process.

17

Typical Procedure for the Palladium-Catalyzed Hydro-arylation of Norbornene Derivatives with Arenediazo-nium Tetrafluoroborates - Hydroarylation of 1a with 2a (Table 2, entry 1)
To a stirred solution of 1a (105.1 mg, 0.50 mmol) and Pd(OAc)2 (5.6 mg, 0.025 mmol) in anhyd THF (4.0 mL), 2a (233.8 mg, 1.0 mmol) was added at r.t. under argon. The reaction mixture was cooled in an ice bath. Then, i-Pr3SiH (205 µL, 1.0 mmol) was added and the reaction mixture was stirred at 15 ˚C for 40 min under argon (the reactor was protected from light with aluminum film). After this time, the mixture was diluted with EtOAc, washed with H2O, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by chromatography on silica gel [n-hexane-EtOAc, 90:10 (v/v)] to afford 120.8 mg (73% yield) of 3a, mp 64-66 ˚C. IR (KBr): 2968, 1735, 1198 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.89 (d, J = 8.2 Hz, 2 H), 7.38 (d, J = 8.2 Hz, 2 H), 3.70 (s, 6 H), 3.64 (t, J = 7.4 Hz, 1 H), 3.19 (ddd, J 1 = 11.7 Hz, J 2 = 4.5 Hz, J 3 = 1.4 Hz, 1 H), 2.99 (dd, J 1 = 11.8 Hz, J 2 = 3.7 Hz, 1 H), 2.75-270 (m, 1 H), 2.73-2.58 (m, 1 H), 2.13 (ddd, J 1 = 11.1 Hz, J 2 = 8.8 Hz, J 3 = 3.7 Hz, 1 H), 1.74-1.65 (m, 2 H), 1.42-1.26 (m, 1 H). ¹³C NMR (100.6 MHz, CDCl3): δ = 197.9, 172.9, 172.6, 151.9, 134.9, 128.5, 127.5, 51.7, 51.5, 47.7, 46.2, 45.9, 41.6, 40.2, 37.5, 33.2, 26.6. MS: m/z (relative intensity) = 330 (12) [M+], 298 (10), 270 (57), 185 (232), 43 (100).

18

NOESY experiments on 3a: for selected H-H interactions, see Figure  [²] .

Figure 2

20

Palladium-Catalyzed Hydroarylation of 1a with 2a Generated In Situ
A solution of BF3˙OEt2 (140 µL, 1.1 mmol) in anhyd THF (1 mL) was cooled at -15 ˚C and p-aminoacetophenone (135.1 mg, 1 mmol) was added. Then, tert-butyl nitrite (160 µL, 1.3 mmol) in 1 mL of the same solvent was added dropwise to the rapidly stirred reaction solution over a period of 10 min. Following complete addition, the temperature of the solution was maintained at -15 ˚C for 10 min and subsequently allowed to warm to 5 ˚C in an ice-water bath over a period of 20 min. Then, the reaction mixture was warmed to r.t. and stirred at the same temperature till the starting p-amino-acetophenone was converted into p-acetylbenzenediazo-nium tetrafluoroborate. The reaction mixture was cooled in an ice bath and 1a (105.1 mg, 0.50 mmol), Pd(OAc)2 (5.6 mg, 0.025 mmol), i-Pr3SiH (205 µL, 1.0 mmol), and of anhyd THF (2 mL) were added. The reaction mixture was allowed to warm to 20 ˚C and stirred at that temperature for 6 h under argon (the reactor was protected from light with aluminum film). After this time, the mixture was diluted with EtOAc, washed with H2O, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by chromatography on silica gel [n-hexane-EtOAc, 90:10 (v/v)] to afford 106.3 mg (64% yield) of 3a.