Synlett 2015; 26(08): 1055-1058
DOI: 10.1055/s-0034-1380325
letter
© Georg Thieme Verlag Stuttgart · New York

Intramolecular Radical Cyclization of Vinyl, Aryl and Alkyl Halides Using Catalytic Amount of Bis-tri-n-butyltin Oxide/Sodium Borohydride: A Novel Entry to Functionalized Carbocycles

Tarur Konikkaledom Dinesh
a  Department of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai 600025, India   Email: bala2010@yahoo.com
b  ITC Life Sciences and Technology Centre, ITC Limited, Peenya Industrial Area, Phase I, Bangalore 560058, India   Email: namasivayam.palani@itc.in
,
Namasivayam Palani*
b  ITC Life Sciences and Technology Centre, ITC Limited, Peenya Industrial Area, Phase I, Bangalore 560058, India   Email: namasivayam.palani@itc.in
,
Sengottuvelan Balasubramanian*
a  Department of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai 600025, India   Email: bala2010@yahoo.com
› Author Affiliations
Further Information

Publication History

Received: 11 January 2015

Accepted after revision: 16 February 2015

Publication Date:
17 March 2015 (online)


Abstract

We wish to report a facile method in which a catalytic amount of bis-tri-n-butyltinoxide (TBTO) in the presence of sodium borohydride efficiently brings about the intramolecular radical cyclization of a variety of vinyl, aryl and alkyl halides to their corresponding functionalized bicyclic and tricyclic carbocycle frameworks. The methodology obviates the need for stoichiometric amounts of tin reagent normally required for radical cyclization reactions.

Supporting Information

 
  • References and Notes

  • 1 Disclaimer: ‘All views expressed herein are authors’ views and in no way, expressed or implied, are that of or necessarily represent the positions of ITC Limited, my current employer.’
  • 2 Janardhanam S, Balakumar A, Rajagopalan K. J. Chem. Soc., Perkin Trans. 1 1994; 551
  • 4 Neumann WP. Synthesis 1987; 665
  • 5 Keinan E, Gleize PA. Tetrahedron Lett. 1982; 23: 477
  • 6 Corey EJ, Suggs JW. J. Org. Chem. 1975; 40: 2554
    • 7a Srikrishna A, Nagaraju S, VeeraRaghava Sharma G. J. Chem. Soc., Chem. Commun. 1993; 285
    • 7b Srikrishna A, Viswajanani R, Sattigeri JA. J. Chem. Soc., Chem. Commun. 1995; 469
  • 8 Terstiege I, Malecka RE. Jr. J. Org. Chem. 1999; 64: 342
  • 9 Lapotre D, Deleuze H, Maillard B, Mulholland K. Synth. Commun. 2001; 31: 3207
  • 10 Prince RH. J. Org. Chem. 1959; 1783
  • 11 Hays DS, Scholl M, Fu GC. J. Org. Chem. 1996; 61: 6751
    • 12a Rajamannar T, Balasubramanian KK. Tetrahedron Lett. 1988; 45: 5789
    • 12b Li CJ. Tetrahedron 1996; 52: 5643
    • 12c Some S, Ray JK. Tetrahedron Lett. 2007; 48: 5013
    • 12d Imanishi T, Kurumada T, Maezaki N, Sugiyama K, Iwata C. J. Chem. Soc., Chem. Commun. 1991; 1409
    • 12e Li CJ. Chem. Rev. 2005; 105: 3095
    • 12f Kurono N, Honda E, Komatsu F, Orito K, Tokuda M. Tetrahedron 2004; 60: 1791
  • 13 Ray D, Yasmin N, Sajal MK, Ray P, Urinda S, Anoop A, Ray JK. Synthesis 2013; 45: 1261
  • 14 Jacobson RM, Lahm GP, Clader JW. J. Org. Chem. 1980; 45: 395
  • 15 Paquette LA, Fristad WE, Dime DS, Bailery TR. J. Org. Chem. 1980; 45: 3017
  • 16 Braude EA, Forbes WF. J. Chem. Soc. 1953; 2208
  • 17 Braude EA, Coles JA. J. Chem. Soc. 1952; 1430
  • 18 Baddeley G, Taylor HT, Pickles W. J. Chem. Soc. 1953; 124
  • 19 Jacob TM, Vatekancherry PA, Dev S. Tetrahedron 1964; 20: 2815
  • 20 2-Bromo-1-cyclohexenyl(2-cyclohexenyl)methanol (9): See Figures S1–S3 in the Supporting Information. 1H NMR (300 MHz, CDCl3): δ = 5.95–5.73 (m, 1 H), 5.39 (dd, J = 10.6, 3.0 Hz, 1 H), 4.55 (d, J = 10 Hz, 1 H), 2.25–2.55 (m, 4 H), 1.67–2.02 (m,12 H). 13C NMR (75 MHz, CDCl3): δ = 136.3, 129.7, 126.8, 121.5, 77.4, 38.7, 37.0, 26.0, 25.1, 25.0, 24.8, 22.1, 20.9. HRMS: m/z [M + H] calcd for C13H19BrO: 271.0730; found: 271.0697. 2,3,4,4b,5,6,7,8,8a,9-Decahydro-1H-9-fluorenol (9a): See Figures S4–S6 in the Supporting Information. 1H NMR (600 MHz, CDCl3): δ = 4.20 (d, J = 6 Hz, 1 H), 2.25–2.32 (br q, 1 H), 2.14–2.25 (m, 1 H), 1.83–1.96 (m, 3 H), 1.74–1.83 (m, 1 H), 1.59–1.72 (m, 2 H), 1.52–1.59 (m, 3 H), 1.34–1.51 (m, 4 H), 1.20–1.30 (m, 1 H), 1.09–1.19 (m, 1 H), 0.85–0.98 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 141.9, 136.0, 80.9, 47.3, 43.5, 28.9, 25.4, 23.9, 23.8, 23.1, 23.0, 23.0, 22.9. HRMS: m/z [M]+ calcd for C13H20O: 192.1510; found: 192.1514. 2-Bromo-1-cycloheptenyl(2-cyclohexenyl)methanol (10): See Figures S7–S9 in the Supporting Information. 1H NMR (600 MHz, CDCl3): δ = 5.73–5.80 (m, 1 H), 5.42 (dd, J = 10.6, 3.0 Hz, 1 H), 4.51 (d, J = 10 Hz, 1 H), 2.75–2.85 (m, 2 H), 2.35 (ddd, J = 15, 10, 2 Hz, 1 H), 2.25–2.33 (m, 2 H), 1.94–2.05 (m, 2 H), 1.85–1.94 (m, 1 H), 1.66–1.84 (m, 3 H), 1.40–1.65 (m, 7 H). 13C NMR (75 MHz, CDCl3): δ = 141.6, 129.4, 127.1, 124.6, 78.8, 41.7, 38.8, 31.7, 28.0, 26.2, 25.3, 25.1, 25.1, 21.0. HRMS: m/z [M – H] calcd for C14H21BrO: 283.0660; found: 283.0697. 2,3,4,4a,5,6,7,8,9,10,10a-Dodecahydrobenzo (a)azulen-10-ol (10a): See Figures S10 and S11 in the Supporting Information. 1H NMR (600 MHz, CDCl3): δ = 4.20 (d, J = 6 Hz, 1 H), 2.32 (dd, J = 16, 8 Hz, 1 H), 2.14–2.20 (m, 1 H), 1.95–2.12 (m, 3 H), 1.84–1.90 (m, 1 H), 1.62–1.72 (m, 2 H), 1.38–1.62 (m, 9 H), 1.15–1.26 (m, 1 H), 1.04–1.12 (m, 1 H), 0.86–0.91 (m, 1 H), 0.84 (br. s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 146.5, 138.6, 82.6, 47.3, 46.0, 31.1, 29.4, 29.1, 27.7, 27.5, 27.0, 25.0, 23.9, 22.8. HRMS: m/z [M + K] calcd for C14H22OK: 245.1308; found: 245.1320.
  • 21 Stork G, Mook RJr, Biller SA, Rychnovsky SD. J. Am. Chem. Soc. 1983; 105: 3741
  • 22 Kreis LM, Krautwald S, Pfeiffer N, Martin RE, Carreira EM. Org. Lett. 2013; 15: 1634
  • 23 Denmark SE, Klix RC. Tetrahedron 1988; 44: 4043