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Synlett 2006(13): 2021-2026  
DOI: 10.1055/s-2006-948182
LETTER
© Georg Thieme Verlag Stuttgart · New York

An Environmentally Friendly Synthesis of Functionalized Indanes Using Electrochemical Cyclization of ortho-Halo-Substituted Homoallyl Ethers and Esters

Sandra Oliveroa, Rodolphe Perriota, Elisabet Duñach*a, Ashvin R. Barub, Eric D. Bellb, Ram S. Mohan*b
a Laboratoire des Molécules Bioactives et des Arômes, CNRS, UMR 6001, Université de Nice-Sophia Antipolis, 06108 Nice Cedex 2, France
e-Mail: dunach@unice.fr;
b Laboratory for Environmentally Friendly Organic Synthesis, Department of Chemistry, Illinois Wesleyan University, Bloomington, IL 61701, USA
e-Mail: rmohan@iwu.edu;
Further Information

Publication History

Received 3 February 2006
Publication Date:
09 August 2006 (online)

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Abstract

The electrochemical cyclization of a series of ortho-halo-substituted homoallyl ethers and esters to functionalized ­indanes catalyzed by Ni(II) catalyst precursors derived from ­Ni(cyclam)Br2, (cyclam = 1,4,8,11-tetraazacyclotetradecane) and Ni(tmc)Br2, (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclo­tetradecane) is reported. The starting homoallyl ethers were synthesized using either a one-pot method for allylation of aldehydes or by direct allylation of the corresponding acetals using bismuth triflate as a catalyst. The remarkably low toxicity, low cost and ease of handling of bismuth salts coupled with the mild nature of the electrochemical procedure makes this approach to indane synthesis especially environmentally friendly and attractive.

Key words

bismuth - electrochemical cyclization - homoallyl ethers - indanes - Ni(II) cyclam

    References and Notes

  • 1a Giese B. In Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds   Pergamon Press; Oxford: 1986. 
    Google Scholar
  • 1b Stork G. In Radical-Mediated Cyclization Processes - A Goal for Synthetic Efficiency   Bartmann W. Trost BM. Verlag Chemie; Basel: 1984. 
    Google Scholar
  • 2a Majumdar KC. Basu PK. Mukhopadhyay PP. Tetrahedron  2004,  60:  6239 
    CrossrefGoogle Scholar
  • 2b Davies AG. Organotin Chemistry   2nd ed.:  Wiley and Sons; London: 2004. 
    CrossrefGoogle Scholar
  • 3 Duñach E. Franco D. Olivero S. Eur. J. Org. Chem.  2003,  1605 
    CrossrefGoogle Scholar
  • 4 Olivero S. Rolland J.-P. Duñach E. Organometallics  1998,  17:  3747 
    CrossrefGoogle Scholar
  • 5a Hong B.-C. Sarshar S. Org. Prep. Proced. Int.  1999,  1:  1 
    Google Scholar
  • 5b Wickens P, Cantin L.-D, Chuang C.-Y, Dai M, Hentemann MF, Kumarasinghe E, Liang SX, Lowe DB, Shelekhin TE, Wang Y, Zhang C, Zhang H.-J, and Zhao Q. inventors; PCT Int. Appl., WO  2004011446. 
  • 5c Sekiguchi T, Nakagawa S, and Fujikura Y. inventors; JP  03044337. 
  • 5d Meakins SE, and Motion KR. inventors; Eur. Pat. Appl., EP  393742. 
  • 5e Frank WC. inventors; USA, US  93-79008. 
  • 5f Ohnuma H, Fujikura Y, Fujita M, and Toi N. inventors; Eur. Pat. Appl., EP  385497. 
  • 5g Sprecker MA, Weiss RA, Belko RP, and Molner EA. inventors; USA, US  6342612. 
  • 6a Wickens P, Cantin L.-D, Chuang C.-Y, Dai M, Hentemann MF, Kumarasinghe E, Liang SX, Lowe DB, Shelekhin TE, Wang Y, Zhang C, Zhang H.-J, and Zhao Q. inventors; PCT Int. Appl., WO  2004011446. 
  • 6b Sekiguchi T, Nakagawa S, and Fujikura Y. inventors; JP  03044337. 
  • 6c Meakins SE, and Motion KR. inventors; Eur. Pat. Appl., EP  393742. 
  • 6d Frank WC. inventors; USA, US  93-79008. 
  • 7 Anzalone PW. Baru AR. Danielson EM. Hayes PD. Nguyen MP. Panico AF. Smith RC. Mohan RS. J. Org. Chem.  2005,  70:  2091 
    CrossrefGoogle Scholar
  • 8a Reglinski J. In Chemistry of Arsenic, Antimony and Bismuth   Norman NC. Blackie Academic and Professional; New York: 1998.  p.403-440  
    CrossrefGoogle Scholar
  • 8b Organobismuth Chemistry   Suzuki H. Matano Y. Elsevier; Amsterdam: 2001. 
    CrossrefGoogle Scholar
  • 8c Leonard NM. Wieland LC. Mohan RS. Tetrahedron  2002,  58:  8373 
    CrossrefGoogle Scholar
  • 8d Antoniotti S. Synlett  2003,  1566 
    CrossrefGoogle Scholar
  • 8e Gaspard-Iloughmane H. Le Roux C. Eur. J. Org. Chem.  2004,  2517 
    CrossrefGoogle Scholar
  • 9 Bosnich B. Tobe ML. Webb GA. Inorg. Chem.  1965,  4:  1109 
    CrossrefGoogle Scholar
  • 10 Gosden C. Healy KP. Pletcher D. J. Chem. Soc., Dalton Trans.  1978,  8:  972 
    Google Scholar
  • 11 Duñach E. Esteves AP. Medeiros MJ. Olivero S. New J. Chem.  2005,  4:  633 
    Google Scholar
  • 12 Armstrong DW. Gahm KH. Chang LW. Microchem. J.  1997,  57:  149 
    CrossrefGoogle Scholar
  • 13 Izumi T. Murakami S. J. Chem. Technol. Biotechnol.  1994,  60:  23 
    CrossrefGoogle Scholar
  • 14 Miura M. Yoshida M. Nojima M. Kusabayashi S. J. Chem. Soc., Perkin Trans. 1  1982,  1:  79 
    Google Scholar
  • 15 Yadav JS. Subba Reddy VB. Srihari P. Synlett  2001,  673 
    Google Scholar
  • 16 Watahiki T. Akabane Y. Mori S. Oriyama T. Org. Lett.  2003,  5:  3045 
    CrossrefPubMedGoogle Scholar
  • 17 Hosomi A. Masahiko E. Sakurai H. Chem. Lett.  1976,  941 
    CrossrefGoogle Scholar
  • 18 Aggarwal VK. Vennall GP. Synthesis  1998,  1822 
    Article in Thieme ConnectGoogle Scholar
  • 19a

    Compound 1a (Method A, 76%): 1H NMR: δ = 1.79 (t, 3 H, J = 7.2 Hz), 2.42-2.46 (m, 2 H), 3.35-3.39 (m, 2 H), 4.72-4.73 (m, 1 H), 5.01-5.10 (m, 2 H), 5.83-5.89 (m, 1 H), 7.25-7.52 (m, 4 H). 13C NMR (12 peaks): δ = 14.8, 40.7, 64.1, 79.4, 116.4, 122.5, 127.1, 127.2, 128.2, 132.1, 134.2, 141.1. HRMS: m/e calcd for C12H15BrO: 254.0306 [M]; found: 253.0231 [M - 1].

  • 19b

    Compound 1b (Method A, 88%): 1H NMR: δ = 2.45 (m, 2 H), 3.24 (s, 3 H), 4.65 (dd, 1 H), 5.07 (m, 2 H), 5.85 (dp, 1 H), 7.42 (m, 4 H). 13C NMR (11 peaks): δ = 41.0, 50.9, 81.7, 117.0, 123.1, 127.5, 127.6, 128.8, 132.6, 134.4, 140.7. HRMS: m/e calcd for C11H13BrO: 240.0150 [M]; found: 239.0066 [M - 1].

  • 19c

    Compound 1c (Method D, 27%): 1H NMR: δ = 2.09 (s, 3 H), 2.55-2.60 (m, 2 H), 5.04-5.10 (t, 2 H, J = 6.43 Hz), 5.72-5.78 (m, 1 H), 6.12-6.15 (dd, 1 H, J = 7.67, 2.73 Hz), 7.09-7.54 (m, 4 H). 13C NMR (12 peaks): δ = 21.0, 39.5, 73.8, 118.1, 122.0, 127.2, 127.4, 129.0, 132.7, 132.9, 139.6, 169.7. HRMS: m/e calcd for C12H13BrO2: 268.0099 [M]; found: 268.0098 [M - 1].

  • 19d

    Compound 1d (Method C, 27%): 1H NMR: δ = 2.48 (t, 2 H, J = 6.9 Hz), 4.28-4.48 (dd, 2 H), 4.86 (t, 1 H, J = 6.18 Hz), 5.02-5.10 (m, 2 H), 5.81-5.94 (m, 1 H), 7.12-7.55 (m, 9 H). 13C NMR (15 peaks): δ = 41.2, 70.9, 79.6, 117.1, 123.1, 127.6, 127.7 (2 peaks), 127.9, 128.3, 128.9, 132.7, 134.5, 138.2, 141.0. HRMS: m/e calcd for C17H17BrO: 316.0463 [M]; found: 315.0381 [M - 1].

  • 19e

    Compound 1e (Method C, 77%): 1H NMR: δ = 1.18 (t, 3 H, J = 7.18 Hz), 2.42-2.46 (m, 2 H), 3.36-3.39 (m, 2 H), 4.76-4.80 (m, 1 H), 5.00-5.10 (m, 2 H), 5.79-5.92 (m, 1 H), 7.16-7.50 (m, 4 H). 13C NMR (12 peaks): δ = 14.7, 40.6, 64.1, 77.1, 116.3, 126.5, 126.9, 127.8, 128.8, 132.3, 134.2, 139.6. HRMS: m/e calcd for C12H15ClO: 210.0811 [M]; found: 209.0740 [M - 1].

  • 19f

    Compound 1f (Method B, 81%): this compound has been reported previously. [15] The spectral data are given here. 1H NMR: δ = 2.46 (m, 2 H), 3.22 (s, 3 H), 4.70 (dd, 1 H, J = 7.3, 4.9 Hz), 5.02 (m, 2 H), 5.86 (m, 1 H), 7.32 (m, 4 H). 13C NMR: (11 peaks): δ = 40.9, 56.9, 79.4, 116.9, 126.9, 127.2, 128.3, 129.3, 132.8, 134.3, 139.1.

  • 19g

    Compound 1g (Method D, 33%): this compound has been reported previously. [15] The spectral data are given here. 1H NMR: δ = 2.09 (s, 3 H), 2.54-2.62 (m, 2 H), 5.03-5.10 (t, 2 H, J = 6.18 Hz), 5.68-5.81 (m, 1 H), 6.18-6.23 (dd, 1 H, J = 7.7, 2.5 Hz), 7.19-7.41 (m, 4 H). 13C NMR (12 peaks): δ = 20.9, 39.4, 71.6, 118.1, 126.8, 127.1, 128.7, 129.5, 132.0, 132.9, 137.9, 169.7.

  • 19h

    Compound 1h (Method C, 35%): 1H NMR: δ = 2.50 (app t, 2 H), 4.38 (dd, 2 H), 4.91 (t, 1 H, J = 6.2 Hz), 5.02 (m, 1 H), 5.90 (dquar, 2 H), 7.30 (m, 9 H). 13C NMR (15 peaks): δ = 41.1, 70.9, 77.2, 117.0, 127.0, 127.5, 127.6, 127.7, 128.3, 128.4, 129.3, 132.9, 134.4, 138.2, 139.4. HRMS: m/e calcd for C17H17ClO: 272.0968 [M]; found: 271.0894 [M - 1].

  • 19i

    Compound 1i (Method A, 43%): 1H NMR: δ = 1.18 (t, 3 H, J = 7.18 Hz), 1.84 (s, 3 H), 2.26-2.42 (m, 2 H), 3.32-3.42 (m, 2 H), 4.78-4.85 (m, 3 H), 7.08-7.52 (m, 4 H). 13C (13 peaks): δ = 15.3, 22.9, 45.2, 64.6, 79.1, 112.4, 123.0, 127.6, 127.7, 128.6, 132.6, 142.1, 142.6. HRMS: m/e calcd for C13H17BrO: 268.0463 [M]; found: 267.0379 [M - 1].