Radical-chain racemisation of tetrahydrofurfuryl acetate under conditions of polarity-reversal catalysis: possible implications for the radical-induced strand cleavage of DNA

Abstract

Alkanethiols with electron-withdrawing S-alkyl groups and silanethiols act as polarity-reversal catalysts to promote the radical-chain racemisation of (R)-tetrahydrofurfuryl acetate at 60 °C, while simple alkanethiols are ineffective.

References

1. For recent relevant papers, see B. Giese, X. Beyrich-Graf, P. Erdmann, M. Petretta and U. Schwitter, Chem. Biol., 1995, 2, 367; A. Gugger, R. Batra, P. Rzadek, G. Rist and B. Giese, J. Am. Chem. Soc., 1997, 119, 8740; B. Giese, A. Dussy, E. Meggers, M. Petretta and U. Schwitter, J. Am. Chem. Soc., 1997, 119, 11 130; S. Peukert, R. Batra and B. Giese, Tetrahedron Lett., 1997, 38, 3507; D. Crich and X.-S. Mo, Tetrahedron Lett., 1997, 38, 8169; D. Crich and Q. Yao, Tetrahedron, 1998, 54, 305.
2. J. Stubbe and J. W. Kozarich, Chem Rev., 1987, 87, 1107; J. Stubbe, J. W. Kozarich, W. Wu and D. E. Vanderwall, Acc. Chem. Res., 1996, 29, 322; A. P. Breen and J. A. Murphy, J. Chem. Soc., Perkin Trans. 1, 1993, 2979.
3. (a) B. P. Roberts and A. J. Steel, J. Chem. Soc., Perkin Trans. 2, 1994, 2155; (b) B. P. Roberts, J. Chem. Soc., Perkin Trans. 2, 1996, 2719.
4. (a) V. Paul and B. P. Roberts, J. Chem. Soc., Chem. Commun., 1987, 1322; (b) V. Paul and B. P. Roberts, J. Chem. Soc., Perkin Trans. 2, 1988, 1183; (c) H.-S. Dang and B. P. Roberts, J. Chem. Soc., Perkin Trans. 1, 1993, 891; (d) P. L. H. Mok, B. P. Roberts and P. T. McKetty, J. Chem. Soc., Perkin Trans. 2, 1993, 665; (e) H.-S. Dang, V. Diart, B. P. Roberts and D. A. Tocher, J. Chem. Soc., Perkin Trans. 2, 1994, 1039.
5. (a) R. P. Allen, B. P. Roberts and C. R. Willis, J. Chem. Soc., Chem. Commun., 1989, 1387; (b) J. N. Kirwan, B. P. Roberts and C. R. Willis, Tetrahedron Lett., 1990, 31, 5093; (c) S. J. Cole, J. N. Kirwan, B. P. Roberts and C. R. Willis, J. Chem. Soc., Perkin Trans. 1, 1991, 103; (d) H.-S. Dang and B. P. Roberts, Tetrahedron Lett., 1995, 36, 2875; (e) M. B. Haque and B. P. Roberts, Tetrahedron Lett., 1996, 37, 9123; (f) H.-S. Dang and B. P. Roberts, J. Chem. Soc., Perkin Trans. 1, 1998, 67.
6. M. P. Balfe, M. Irwin and J. Kenyon, J. Chem. Soc., 1941, 312 (R)-(—)-Tetrahydrofurfuryl alcohol, which showed [α]²⁰_D–2.3 (neat, d= 1.054), was obtained from Kiralchem Ltd., 17 Canalside, 2–4 Orsman Road, London N1 5QJ. It was converted to the acetate by treatment with Ac₂O in the presence of NEt₃.
7. (a) H. Kiefer and T. G. Traylor, Tetrahedron Lett., 1966, 6163; (b) G. D. Mendenhall, Tetrahedron Lett., 1983, 24, 451.
8. J. A. Baban and B. P. Roberts, J. Chem. Soc., Perkin Trans. 2, 1981, 161; V. Diart and B. P. Roberts, J. Chem. Soc., Perkin Trans. 2, 1992, 1761; B. P. Roberts and A. J. Steel, J. Chem. Soc., Perkin Trans. 2, 1992, 2025.
9. S. Rockwell, Oncol. Res., 1997, 9, 383.