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Synlett 2009(17): 2815-2820  
DOI: 10.1055/s-0029-1217998
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Bismuth(III)-Promoted C3-Ferrocenyl Alkylation of Indoles

Ran Jiang, Xiao-Ping Xu*, Tao Chen, Hong-Yun Li, Gang Chen, Shun-Jun Ji*
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Renai Road Suzhou Industrial Park, Suzhou 215123, P. R. of China
Fax: +86(512)65880307; e-Mail: chemjsj@suda.edu.cn; e-Mail: xuxp@suda.edu.cn;
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Publication History

Received 23 June 2009
Publication Date:
30 September 2009 (online)

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Abstract

Reaction of α-ferrocenyl alcohols with indoles in acetonitrile in the presence of Bi(NO3)3˙5H2O afforded 3-alkylated indole derivatives in good yields and high selectivity. Bi(NO3)3˙5H2O proved to be an efficient catalyst in such a transformation.

Key words

bismuth(III) nitrate - ferrocenyl alcohols - indole

    References and Notes

  • 1a Joule JA. Mills K. Heterocyclic Chemistry   4th ed.:  Blackwell Science; Oxford: 2000. 
    Google Scholar
  • 1b Sundberg RJ. Indoles   Academic Press; London: 1996. 
    Google Scholar
  • 1c Horton DA. Bourne GT. Smythe ML. Chem. Rev.  2003,  103:  893 
    Google Scholar
  • 1d Humphrey GR. Kuethe JT. Chem. Rev.  2006,  106:  2875 
    Google Scholar
  • For selected examples, see:
  • 2a Yasuda M. Somyo T. Baba A. Angew. Chem. Int. Ed.  2006,  45:  793 
    Google Scholar
  • 2b Yadav JS. Reddy BVS. Raghavendra KV. Kumar CGKSN. Tetrahedron Lett.  2007,  48:  3295 
    Google Scholar
  • 2c Jana U. Maiti S. Biswas S. Tetrahedron Lett.  2007,  48:  7160 
    Google Scholar
  • 2d Nishibayashi Y. Yoshikawa M. Inada Y. Hidai M. Uemura S. J. Am. Chem. Soc.  2002,  124:  11846 
    Google Scholar
  • 2e Inada Y. Yoshikawa M. Milton MD. Nishibayashi Y. Uemura S. Eur. J. Org. Chem.  2006,  881 
    Google Scholar
  • 2f Cheung HY. Yu WY. Lam FL. Au-Yeung TT.-L. Zhou ZY. Chan TH. Chan ASC. Org. Lett.  2007,  9:  4295 
    Google Scholar
  • 2g Yadav JS. Reddy BVS. Aravind S. Kumar GGKSN. Reddy AS. Tetrahedron Lett.  2007,  48:  6117 
    Google Scholar
  • 2h Tabatabaeian K. Mamaghani M. Mahmoodi NO. Khorshidi A. Tetrahedron Lett.  2008,  49:  1450 
    Google Scholar
  • 2i Cincinelli R. Dallavalle S. Merlini L. Synlett  2008,  1309 
    Google Scholar
  • 2j Liu YH. Liu QS. Zhang ZH. Tetrahedron Lett.  2009,  50:  916 
    Google Scholar
  • Some examples have been presented by Cozzi et al., see:
  • 3a Saito T. Nishimoto Y. Yasuda M. Baba A. J. Org. Chem.  2006,  71:  8516 
    Google Scholar
  • 3b Cozzi PG. Zoli L. Green Chem.  2007,  9:  1292 
    Google Scholar
  • 3c Cozzi PG. Vicennati P. Eur. J. Org. Chem.  2007,  2248 
    Google Scholar
  • 3d Cozzi PG. Zoli L. Angew. Chem. Int. Ed.  2008,  47:  4162 
    Google Scholar
  • 4a Togni A. Hayashi T. Ferrocenes: Homogeneous Catalysis, Organic Synthesis, Materials Science   VCH; Weinheim: 1995. 
    Google Scholar
  • 4b Štěpnička P. Ferrocenes: Ligands, Materials and Biomolecules   John Wiley and Sons Ltd; West Sussex: 2008. 
    Google Scholar
  • 4c Diallo AK. Daran JC. Varret F. Ruiz J. Astruc D. Angew. Chem. Int. Ed.  2009,  48:  3141 
    Google Scholar
  • 5a Nugent MJ. Kummer R. Richards JH. J. Am. Chem. Soc.  1969,  91:  6141 
    Google Scholar
  • 5b Nugent MJ. Carter RE. Richards JH. J. Am. Chem. Soc.  1969,  91:  6145 
    Google Scholar
  • 5c Marquarding D. Klusacek H. Gokel G. Hoffman P. Ugi I. J. Am. Chem. Soc.  1970,  92:  5389 
    Google Scholar
  • 5d Gokel G. Marquarding D. Ugi I. J. Org. Chem.  1972,  37:  3052 
    Google Scholar
  • 5e Seo H. Kim BY. Lee JH. Park HJ. Son SU. Chung YK. Organometallics  2003,  22:  4783 
    Google Scholar
  • 5f Gleiter R. Bleiholder C. Rominger F. Organometallics  2007,  26:  4850 
    Google Scholar
  • 6a Ji SJ. Wang SY. Synlett  2003,  2074 
    Google Scholar
  • 6b Wang SY. Ji SJ. Loh TP. Synlett  2003,  2377 
    Google Scholar
  • 6c Ji SJ. Wang SY. Zhang Y. Loh TP. Tetrahedron  2004,  60:  2051 
    Google Scholar
  • 6d Gu DG. Ji SJ. Jiang Z.-Q. Zhou M.-F. Loh TP. Synlett  2005,  959 
    Google Scholar
  • 6e Wang SY. Ji SJ. Tetrahedron  2006,  62:  1527 
    Google Scholar
  • 6f Wang SY. Ji SJ. Synlett  2007,  2222 
    Google Scholar
  • 6g Zhu SL. Ji SJ. Zhang Y. Tetrahedron  2007,  63:  9365 
    Google Scholar
  • 6h Zhu S.-L. Ji S.-J. Zhao K. Liu Y. Tetrahedron Lett.  2008,  49:  2578 
    Google Scholar
  • 7a Ji SJ. Shen ZL. Gu DG. Wang SY. J. Organomet. Chem.  2004,  689:  1843 
    Google Scholar
  • 7b Yang JM. Ji SJ. Gu DG. Shen ZL. Wang SY. J. Organomet. Chem.  2005,  690:  2989 
    Google Scholar
  • 7c Zhou WJ. Ji SJ. Shen ZL. J. Organomet. Chem.  2006,  691:  1356 
    Google Scholar
  • 8 Xu XP. Jiang R. Zhou XG. Liu Y. Ji SJ. Zhang Y. Tetrahedron  2009,  65:  877 
    CrossrefGoogle Scholar
  • 9a Samajdar S. Becker FF. Banik BK. Tetrahedron Lett.  2000,  41:  8017 
    Google Scholar
  • 9b Aggen DH. Arnold JN. Hayes PD. Smoter NJ. Mohan RS. Tetrahedron  2004,  60:  3675 
    Google Scholar
  • 9c Mohammadpoor-Baltork I. Khodaei MM. Nikoofar K. Tetrahedron Lett.  2003,  44:  591 
    Google Scholar
  • 9d Evans PA. Andrews WJ. Tetrahedron Lett.  2005,  46:  5625 
    Google Scholar
  • 10a Thirupathi P. Kim SS. Tetrahedron  2009,  65:  5168 
    Google Scholar
  • 10b Bhattacharya AK. Kaur T. Synlett  2007,  745 
    Google Scholar
  • 10c Srivastava N. Dasgupta SK. Banik BK. Tetrahedron Lett.  2003,  44:  1191 
    Google Scholar
  • 10d Banik BK. Cardonar M. Tetrahedron Lett.  2006,  47:  7385 
    Google Scholar
  • 10e Banik BK. Reddy AT. Datta A. Mukhopadhyay C. Tetrahedron Lett.  2007,  48:  7392 
    Google Scholar
  • 10f Cunha S. Rodrigues MT. Tetrahedron Lett.  2006,  47:  6955 
    Google Scholar
11

Crystallographic data for the structure of 2c reported in this paper has been deposited at the Cambridge Crystallographic Data Centre as supplementary publication with No. CCDC 735976, respectively. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [E-mail: linstead@ccdc.cam.ac.uk or deposit@ccdc.cam.ac.uk; fax: +44 (1223)336033].
Structural Parameters for 2c: Data collection: Rigaku Mercury CCD area detector; crystal size: 0.48 × 0.26 × 0.10 mm³; C32H27FeNO, Mr = 497.40, triclinic, space group P -1, a = 9.2490 (9), b = 11.0210 (15), c = 13.668 (2) Å, α = 82.363 (18), β = 70.362 (14), γ = 67.930 (13)˚, V = 1216.0(3) ų, Z = 2, D calcd = 1.358 g cm-³, R [I > 2σ(I)] = 0.0746, wR [I > 2σ(I)] = 0.1185.

12

General Experimental Procedure: A mixture of α-ferrocenyl ethanol (1, 0.058 g, 0.25 mmol), indole 7a (0.029 g, 0.25 mmol), and Bi(NO3)3˙5H2O (0.006 g, 0.0125 mmol) in MeCN (2 mL) was stirred in flash at r.t. until 1 was completely consumed (1 h, checked by TLC). Then the solvent was evaporated under the reduced pressure. The residue was purified by flash column chromatography with EtOAc and PE as eluents to afford product 1a (0.078 g, yield 95%).
4-Methyl-3-(ferrocenylethyl)-1 H -indole (1d): Orange solid; mp 139.9-140.7 ˚C. IR (KBr): 3059, 2957, 1706, 1448, 1105 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 1.67 (d, J = 4.4 Hz, 3 H), 2.75 (s, 3 H), 4.13-4.18 (m, 9 H), 4.37 (q, J = 6.0 Hz, 1 H), 6.66 (s, 1 H), 6.86 (d, J = 6.4 Hz, 1 H), 7.05 (t, J = 7.2 Hz, 1 H), 7.17 (d, J = 7.6 Hz, 1 H), 7.05 (br s, 1 H, NH). ¹³C NMR (100 MHz, CDCl3): δ = 136.8, 130.9, 125.6, 125.2, 122.2, 121.7, 109.6, 96.1, 68.9, 68.2, 67.9, 67.3, 67.0, 31.4, 24.0, 21.0. HRMS (EI): m/z calcd for C21H21NFe: 343.1023; found: 343.1025.