View PDF Version
 
DOI: 10.1039/A901484E (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1999, 2383-2390

Face selectivity in the reactions of Grignard reagents with 5-substituted-2-dicyanomethyleneadamantanes

(Note: The full text of this document is currently only available in the PDF Version )

Kuo-Hsi Kao, Ren-Shyang Sheu, Yuh-Shih Chen, Wen-Wei Lin, Ju-Tsung Liu and Ching-Fa Yao

Abstract

Reactions of 5-substituted-2-dicyanomethyleneadamantanes (4-Z) with benzylmagnesium bromide (C6H5CH2MgBr) or alkylmagnesium halides (RMgX) generated the 1,4-addition (5-Z (R)) and/or the hydrogenation (5-Z (H)) products. A variety of substituents X were used: hydro, fluoro, chloro, bromo and phenyl groups. The generation of the different isomeric products from the zu-face or en-face by the transfer of the benzyl or alkyl groups, or the hydride from the Grignard reagents is discussed in terms of the electrostatic field influence and the steric hindrance between the Grignard reagents and the substrate 4-Z. Reactions of 4-Br or 4-Ph with phenylmagnesium bromide generated 1,2-addition products 6-Br, 7-Br or 8-Ph when the intermediate A was added to dry methanol or to dilute ice-cold hydrochloric acid solution.

References

  1. (a) G. R. N. Jones, Nature (London), 1972, 235, 257 CAS ; (b) A. J. Fatiadi, Synthesis, 1978, 165 CrossRef CAS ; (c) F. Freeman, Chem. Rev., 1980, 329 CrossRef CAS .
  2. (a) N. Latif and N. Mishriky, Can. J. Chem., 1966, 41, 1271 ; (b) N. Latif, I. F. Zeid and F. Assad, Chem. Ind. (London), 1970, 1539 CAS ; (c) N. Latif, N. S. Girgis and F. Michael, Tetrahedron, 1970, 26, 5765 CrossRef CAS ; (d) N. Latif, N. Mishriky and K. A. Mohsen, J. Chem. Soc., Perkin Trans. 1, 1974, 875 RSC .
  3. (a) C. K. Cheung, L. T. Tseng, M.-H. Lin, S. Srivastava and W. J. le Noble, J. Am. Chem. Soc., 1986, 108, 1598 CrossRef CAS ; (b) V. R. Bodepudi and W. J. le Noble, J. Org. Chem., 1991, 56, 2001; 1994, 59, 3265 Search PubMed ; (c) W.-S. Chung, T.-L. Tsai, C.-C. Ho, M. N. N. Chiang and W. J. le Noble, J. Org. Chem., 1997, 62, 4672 CrossRef CAS ; (d) J. M. Coxon, K. N. Houk and R. T. Luibrand, J. Org. Chem., 1995, 60, 418 CrossRef CAS  and references cited therein.
  4. (a) A. S. Cieplak, J. Am. Chem. Soc., 1981, 103, 4540 CrossRef CAS ; (b) C. R. Johnson, B. D. Tait and A. S. Cieplak, J. Am. Chem. Soc., 1987, 109, 5875 CrossRef CAS ; (c) A. S. Cieplak, B. D. Tait and C. R. Johnson, J. Am. Chem. Soc., 1989, 111, 8447 CrossRef CAS .
  5. (a) W. Adcock, J. Cotton and N. A. Trout, J. Org. Chem., 1994, 59, 1867 CrossRef CAS ; (b) W. Adcock, J. Cotton and N. A. Trout, J. Org. Chem., 1995, 60, 7074 CrossRef CAS .
  6. W. Adcock, N. J. Head, N. R. Lokan and N. A. Trout, J. Org. Chem., 1997, 62, 6177 CrossRef CAS .
  7. (a) A. Streitwieser, C. H. Heathcock and E. M. Kosower, in Introduction to Organic Chemistry, 4th edn., Macmillan, New York, 1992, p. 403 Search PubMed ; (b) M. B. Smith, in Organic Synthesis, McGraw-Hill, Singapore, 1994, p. 714 Search PubMed ; (c) J. March, in Advanced Organic Chemistry: Reactions, Mechanism and Structure, 4th edn., John Wiley & Sons, New York, 1992, p. 926 Search PubMed .
  8. M.-H. Lin, J. E. Silver and W. J. le Noble, J. Org. Chem., 1988, 53, 5155 CrossRef CAS .
  9. Full crystallographic details, excluding structure factor tables, have been deposited at the Cambridge Crystallographic Data Centre (CCDC). For details of the deposition scheme, see ‘Instruction for Authors’, J. Chem. Soc., Perkin Trans. 1, available via the RSC Web pages (http//www.rsc.org/authors). Any request to the CCDC for this material should quote the literature citation and the reference number 207/337. See http://www.rsc.org/suppdata/p1/1999/2383 for crystallographic .les in .cif format Search PubMed .
  10. M. S. Karasch and O. Reinmuth, Grignard Reactions of Nonmetallic Substrates, Constable, New York, 1954, p. 774 Search PubMed .
  11. E. S. Gould, Mechanism and Structure in Organic Chemistry, Holt, Rinehart and Winston, New York, 1962, p. 403 Search PubMed .
  12. P. L. Pickard and T. J. Tolbert, J. Org. Chem., 1961, 26, 4886 CrossRef CAS .
  13. C.-F. Yao, Y.-S. Chen, W.-C. Chen, R.-S. Sheu, J.-K. Lai and C.-H. Ueng, Acta Crystallogr., Sect. C, 1997, 53, 956 CrossRef .
  14. V. Migrdichian, The Chemistry of Organic Cyanogen Compounds, Reinhold, New York, 1947, p. 254 Search PubMed .
  15. (a) I. Tabushi and Y. Aoyama, J. Org. Chem., 1973, 38, 3447 CAS ; (b) M. Xie and W. J. le Noble, J. Org. Chem., 1989, 54, 3839 CrossRef CAS ; (c) W.-S. Chung, Y.-D. Liu and N.-J. Wang, J. Chem. Soc., Perkin Trans. 2, 1995, 581 RSC ; (d) M. Kaselj, E. M. Gonikberg and W. J. le Noble, J. Org. Chem., 1998, 63, 3218 CrossRef .
  16. H. W. Geluk, Synthesis, 1972, 374 CrossRef CAS .
  17. (a) A. C. Cope and K. E. Hoyle, J. Am. Chem. Soc., 1941, 63, 733 CrossRef CAS ; (b) B. Krijnen, H. B. Beverloo, J. W. Verhoeven, C. A. Reiss, K. Goubitz and D. Heijdenrijk, J. Am. Chem. Soc., 1989, 111, 4433 CrossRef CAS .
  18. A. W. J. D. Dekkers, J. W. Verhoeven and W. N. Speckamp, Tetrahedron, 1973, 29, 1691 CrossRef CAS .
  19. R. van Hes, A. Smit, T. Kralt and A. Peters, J. Med. Chem., 1972, 15, 132 CrossRef CAS .
Click here to see how this site uses Cookies. View our privacy policy here.