Hydrogen bonding and solvent effects in heteroaryldi(1-adamantyl)methanols: an NMR and IR spectroscopic study

Abstract

Reaction of the organolithium derivatives of certain heteroaromatics [2-furanyl, 2-thienyl, 2-thiazolyl, 2-pyridyl and 2-(3-methylpyridyl)] with di(1-adamantyl) ketone gives potentially rotameric tertiary alcohols. With 2-pyridyl- and 2-(3-methylpyridyl)lithium only the syn isomer is obtained. The syn isomer makes up 85–100% of (2-furanyl)diadamantylmethanol and 80–90% of the 2-thienyl derivative, depending on the NMR solvent. In chloroform or benzene the 2-thiazolyl derivative is a 2∶1 mixture, the isomer with the sulfur atom syn to the OH group predominating; in DMSO or in the solid state this is the sole species. The IR absorption frequency for OH stretching correlates with the corresponding proton NMR shift in chloroform and with its temperature dependence, Δ δ/ΔT. In pyridine Δ δ/ΔT is either large (–20 ppb/°C) or small (–1 to –2 ppb/°C) for intermolecular and intramolecular hydrogen-bonded species, respectively. Semi-empirical calculations (AM1 and PM3) suggest that the anti alcohols should be the more stable in the gas phase, but solvent effects and hydrogen bonding, in the case of the pyridyl derivatives, appear to reverse this situation, making the isomer with OH syn to the heteroatom the principal, and sometimes the only, species observed in solution.

References

1. J. S. Lomas and J. Vaissermann, J. Chem. Soc., Perkin Trans. 2, 1998, 1777.
2. (a) J. S. Lomas and J. E. Dubois, Tetrahedron, 1981, 37, 2273; (b) J. S. Lomas and V. Bru-Capdeville, J. Chem. Soc., Perkin Trans. 2, 1994, 459.
3. J. A. Lepoivre, Janssen Chim. Acta, 1991, 9, 20.
4. S. Nomura and T. Hidaka, Jap P 02,300,171 [90,300,171](Chem. Abstr., 1990, 114, 185292k); S. Nomura and T. Hidaka, Jap P 03,56,464 [91,56,464](Chem. Abstr., 1991, 115, 158974y).
5. G. Van Zyl, R. J. Langenberg, H. H. Tan and R. N. Schut, J. Am. Chem. Soc., 1956, 78, 1955.
6. A. Dondoni, G. Fantin, M. Fogagnolo, A. Medici and P. Pedrini, J. Org. Chem., 1988, 53, 1748; A. Dondoni and D. Perrone, J. Org. Chem., 1995, 60, 4749.
7. D. J. Chadwick and C. Willbe, J. Chem. Soc., Perkin Trans. 1, 1977, 887.
8. E. Pretsch, W. Simon, J. Seibl and T. Clerc, Tables of Spectral Data for Structure Determination of Organic Compounds, Springer-Verlag, Berlin-Heidelberg, 2nd edn., 1989.
9. gNMR from Cherwell Scientific Publishing Limited, The Magdalen Centre, Oxford Science Park, Oxford OX4 4GA.
10. R. S. Cahn, C. K. Ingold and V. Prelog, Angew. Chem., 1966, 78, 413.
11. M. D. Joesten and L. J. Schaad, Hydrogen Bonding, Marcel Dekker, New York, 1974; F. Hibbert and J. Emsley, Adv. Phys. Org. Chem., 1990, 26, 255.
12. H. S. Aaron, Top. Stereochem., 1979, 11, 1; M. C. R. Symons, Chem. Soc. Rev., 1983, 12, 1.
13. H. Kessler, Angew. Chem., Int. Ed. Engl., 1982, 21, 512 See also: M. P. Williamson and J. P. Waltho, Chem. Soc. Rev., 1992, 21, 227.
14. L. W. Reeves, E. A. Allan and K. O. Strømme, Can. J. Chem., 1960, 38, 1249; I. Gränacher, Helv. Phys. Acta, 1961, 34, 272; J. R. Merrill, J. Phys. Chem., 1961, 65, 2023; G. O. Dudek, J. Org. Chem., 1965, 30, 548; A. D. Sherry and K. F. Purcell, J. Phys. Chem., 1970, 74, 3535.
15. H. Iwamura, Tetrahedron Lett., 1970, 2227.
16. H. S. Im, E. R. Bernstein, H. V. Secor and J. I. Seeman, J. Am. Chem. Soc., 1991, 113, 4422.
17. F. H. Hon, H. Matsumura, H. Tanida and T. T. Tidwell, J. Org. Chem., 1972, 37, 1778; J. S. Lomas, P. K. Luong and J. E. Dubois, J. Org. Chem., 1977, 42, 3394.
18. J. S. Lomas and J. Vaissermann, Bull. Soc. Chim. Fr., 1996, 133, 25; J. Vaissermann and J. S. Lomas, Acta Crystallogr., Sect. C, 1997, 53, 1341.
19. L. P. Kuhn, R. A. Wires, W. Ruoff and H. Kwart, J. Am. Chem. Soc., 1969, 91, 4790.
20. J. N. Brown, R. M. Jenevein, J. H. Stocker and L. M. Trefonas, J. Org. Chem., 1972, 37, 3712.
21. S. E. Bojadziev, D. T. Tsankov, P. M. Ivanov and N. D. Berova, Bull. Chem. Soc. Jpn., 1987, 60, 2651.
22. L. Re, B. Maurer and G. Ohloff, Helv. Chim. Acta, 1973, 56, 1882.
23. (a) S. H. Gellmann, G. P. Dado, G. B. Liang and B. R. Adams, J. Am. Chem. Soc., 1991, 113, 1164; (b) G. P. Dado and S. H. Gellmann, J. Am. Chem. Soc., 1993, 115, 4228; (c) G. P. Dado and S. H. Gellmann, J. Am. Chem. Soc., 1994, 116, 1054; (d) B. W. Gung and Z. Zhu, J. Org. Chem., 1996, 61, 6482; (e) B. W. Gung and Z. Zhu, J. Org. Chem., 1997, 62, 2324; (f) B. W. Gung, Z. Zhu and B. Everingham, J. Org. Chem., 1997, 62, 3436.
24. Cavitands: D. M. Rudkevich, G. Hilmersson and J. Rebek, J. Am. Chem. Soc., 1997, 119, 9911 Carbohydrates: M. López de la Paz, J. Jiménez-Barbaro and C. Vicent, J. Chem. Soc., Chem. Commun., 1998, 465; M. López de la Paz, G. Ellis, S. Penadés and C. Vicent, Tetrahedron Lett., 1997, 38, 1659; C. Landersjö, R. Stenutz and G. Widmalm, J. Am. Chem. Soc., 1997, 119, 8695.
25. N. L. Allinger, Quantum Chemistry Program Exchange, Program MMP2(85), Indiana University, USA.
26. R. Taylor and O. Kennard, Acc. Chem. Res., 1984, 17, 320.
27. PC Spartan from Wavefunction, Inc., 18401 Von Karman Avenue, Suite 370, Irvine, CA 92612, USA. AM1: M. J. S. Dewar, E. G. Zoebisch, E. F. Healy and J. J. P. Stewart, J. Am. Chem. Soc., 1985, 107, 3902 PM3: J. J. P. Stewart, J. Comput. Chem., 1989, 10, 209.