Synthesis 2006(16): 2748-2752  
DOI: 10.1055/s-2006-942500
PAPER
© Georg Thieme Verlag Stuttgart · New York

Thallium(III)-Mediated Ring Contraction of cis-Octalins: An Approach for the Diastereoselective Construction of the nor-Bakkane Skeleton

Helena M. C. Ferraz*, Tiago O. Vieira, , Jr Luiz F. Silva
Instituto de Química, Universidade de São Paulo, CP 26077, CEP 05513-970, São Paulo SP, Brazil
Fax: +55(11)8155579; e-Mail: hmferraz@iq.usp.br;
Further Information

Publication History

Received 6 April 2006
Publication Date:
19 July 2006 (eFirst)

Abstract

A new approach for the diastereoselective synthesis of cis-hydrindanes bearing important structural features of the bakkane skeleton is described. The key step in such a sequence is a thallium trinitrate mediated oxidative rearrangement of cis-octalins. The ring-contraction products thus obtained were elaborated in a diastereoselective fashion into hydrindanes bearing a quaternary center.

    References

  • 1a Abe N. Onoda R. Shirahata K. Kato T. Woods MC. Kitahara Y. Tetrahedron Lett.  1968,  369 
  • 1b Naya K. Takagi I. Hayashi M. Nakamura S. Kobayashi M. Katsumura S. Chem. Ind. (London)  1968,  318 
  • 2 For a review concerning the chemistry of bakkanes, see: Silva LF. Synthesis  2001,  671 
  • For examples, see:
  • 3a Jamieson GR. Reid EH. Turner BP. Jamieson AT. Phytochemistry  1976,  15:  1713 
  • 3b Kano K. Hayashi K. Mitsuhashi H. Chem. Pharm. Bull.  1982,  30:  1198 
  • 3c Wu T.-S. Kao M.-S. Wu P.-L. Lin F.-W. Shi L.-S. Liou M.-J. Li C.-Y. Chem. Pharm. Bull.  1999,  47:  375 
  • For examples, see:
  • 4a Nawrot J. Bloszyk E. Harmatha J. Novotný L. J. Appl. Entomol.  1984,  98:  394 
  • 4b Nawrot J. Harmatha J. Novotn L. Biochem. Syst. Ecol.  1984,  12:  99 
  • 5 Wu T.-S. Kao M.-S. Wu P.-L. Lin F.-W. Shi L.-S. Teng C.-M. Phytochemistry  1999,  52:  901 
  • 6 Liao C.-H. Ko F.-N. Wu T.-S. Teng C.-M. J. Pharm. Pharmacol.  1997,  49:  1248 
  • 7 Reddy DS. Org. Lett.  2004,  6:  3345 
  • 8a Back TG. Nava-Salgado VO. Payne JE. J. Org. Chem.  2001,  66:  4361 
  • 8b Back TG. Payne JE. Org. Lett.  1999,  1:  663 
  • 9a Srikrishna A. Reddy TJ. Arkivoc  2001,  (viii):  9 
  • 9b Srikrishna A. Nagaraju S. Venkateswarlu S. Hiremath US. Reddy TJ. Venugopalan P. J. Chem. Soc., Perkin Trans. 1  1999,  2069 
  • 9c Hayashi K. Nakamura H. Mitsuhashi H. Chem. Pharm. Bull.  1973,  21:  2806 
  • 10 Mori K. Matsushima Y. Synthesis  1995,  845 
  • 11a Evans DA. Sims CL. Tetrahedron Lett.  1973,  4691 
  • 11b Evans DA. Sims CL. Andrews GC. J. Am. Chem. Soc.  1977,  99:  5453 
  • For some leading references, see:
  • 12a Brocksom TJ. Coelho F. Depres JP. Greene AE. de Lima MEF. Hamelin O. Hartmann B. Kanazawa AM. Wang YY. J. Am Chem. Soc.  2002,  124:  15313 
  • 12b Hamelin O. Wang Y. Depres JP. Greene AE. Angew. Chem. Int. Ed.  2000,  39:  4314 
  • 12c Hamelin O. Deprés J.-P. Greene AE. Tinant B. Declercq J.-P. J. Am. Chem. Soc.  1996,  118:  9992 
  • 12d Greene AE. Deprés J.-P. Coelho F. Brocksom TJ. J. Org. Chem.  1985,  50:  3943 
  • 12e

    For other papers, see, for example: ref. 2 and ref. 12a.

  • 13 Kabbe H.-J. Justus Liebigs Ann. Chem.  1962,  656:  204 
  • 14a Lee JB. Price MJ. Tetrahedron Lett.  1962,  1155 
  • 14b Lee JB. Price MJ. Tetrahedron  1964,  20:  1017 
  • 15 Anderson CB. Winstein S. J. Org. Chem.  1963,  28:  605 
  • For some reviews concerning thallium(III), see:
  • 16a McKillop A. Taylor EC. In Comprehensive Organometallic Chemistry   Vol. 7:  Wilkinson G. Pergamon Press; New York: 1982.  p.465 
  • 16b Ferraz HMC. Silva LF. Vieira Tde O. Synthesis  1999,  2001 
  • 16c McKillop A. Taylor EC. In Organic Synthesis by Oxidation with Metal Compounds   Mijs WJ. De Jonge CRHI. Plenum; New York: 1986.  p.695 
  • 17a For a review concerning thallium(III)-mediated ring-contraction reactions, see: Ferraz HMC. Silva LF. Quim. Nova  2000,  23:  216 
  • 17b For a review concerning ring contraction reactions, see: Silva LF. Tetrahedron  2002,  58:  9137 
  • 18 Ferraz HMC. Silva LF. Tetrahedron  2001,  57:  9939 
  • 19 Ferraz HMC. Silva LF. Vieira TO. Tetrahedron  2001,  57:  1709 
  • 20 Silva LF. Sousa RMF. Ferraz HMC. Aguilar AM. J. Braz. Chem. Soc.  2005,  16:  1160 
  • 21a Ferraz HMC. Aguilar AM. Silva LF. Synthesis  2003,  1031 
  • 21b Ferraz HMC. Aguilar AM. Silva LF. Tetrahedron  2003,  59:  5817 
  • 22 Ferraz HMC. Silva LF. J. Org. Chem.  1998,  63:  1716 
  • 23 Ferraz HMC. Silva LF. J. Braz. Chem. Soc.  2001,  12:  548 
  • 24 2-Methylcyclohex-2-enone was prepared in two steps (bromination followed by dehydrohalogenation) from 2-methylcyclohexanone, in 68% yield: Hua DH. Chen Y. Sin H.-S. Maroto MJ. Robinson PD. Newell SW. Perchellet EM. Ladesich JB. Freeman JA. Perchellet J.-P. Chiang PK. J. Org. Chem.  1997,  62:  6888 
  • 25 Nagakura I. Ogata H. Ueno M. Kitahara Y. Bull. Chem. Soc. Jpn.  1975,  48:  2995 
  • 26 Fringuelli F. Pizzo F. Taticchi A. Halls TDJ. Wenkert E. J. Org. Chem.  1982,  47:  5056 
  • 27 Angell EC. Fringuelli F. Pizzo F. Taticchi A. Wenkert E. J. Org. Chem.  1988,  53:  1224 
  • 28 McKillop A. Hunt JD. Kienzle F. Bigham E. Taylor EC. J. Am. Chem. Soc.  1973,  95:  3635 
  • 29 Abley P. Byrd JE. Halpern J. J. Am. Chem. Soc.  1973,  95:  2591 
  • 30 Sekizaki H. Ito M. Inoue S. Bull. Chem. Soc. Jpn.  1978,  51:  2439 
  • 31 Heathcock CH. Ratcliffe R. Van J. J. Org. Chem.  1972,  37:  1796 
  • 32 Ratcliffe BE. Heathcock CH. J. Org. Chem.  1972,  37:  531 
33

The X-ray data have been deposited at the Cambridge Crystallographic Data Centre and allocated the deposition number CCDC 605577.