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Novel Rearrangement of Tertiary Fenchyl Alcohols with Sulfuric Acid in Acetonitrile

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Warianty tytułu
Języki publikacji
EN
Abstrakty
EN
The influence of steric hindrance on rearrangements of tertiary 2-fenchyl cations under the Ritter reaction conditions (CH3CN/H2SO4) has been described. Depending on the branching of alkyl substituents at the C-2 position, the reaction time and temperature, different reaction courses have been observed. After 10 minutes at -20 to -15°C alcohol 2 (R = iso-Am) gave alkenes 7, whereas a pair of amides 8 and 9 for 24 hours at ambient temperature as a result of successive exo-3,2-methyl shift,Wagner-Meerwein rearrangement and endo-6,2-hydride shift. Alkene 10 was obtained as a primary product from alcohol 3 (R = iso-Bu) after 10 minutes at -20 to -15°C. When the same reaction was continued for 24 hours at room temperature, amide 12 has been obtained as the only product. It was explained by the operation of endo-6,2-hydride shift after protonation of alkene 10 and further reaction with acetonitrile. In the case of alcohols 4-6 with bulky isopropyl, sec-butyl and 2-sec-amyl substituents, a novel rearrangement to tetrasubstituted alkenes containing the bicyclo[3.1.1]heptane skeleton have been notified. The mechanistic proposals for the investigated reaction are presented.
Słowa kluczowe
Rocznik
Strony
37--44
Opis fizyczny
Bibliogr. 18 poz., rys.
Twórcy
autor
  • Faculty of Chemistry, Nicolaus Copernicus University, 87-100 Torun, Poland
Bibliografia
  • 1. Sorensen T.C., Acc. Chem. Res., 9, 257 (1976) and references therein.
  • 2. Toivonen M., Tetrahedron Lett., 3041 (1968).
  • 3. Antkowiak W.Z., Bull. Acad. Pol. Sci. Ser. Sci. Chim., 14,437 (1966).
  • 4. Barrow C.J., Bright S.T., Coxon J.M. and Steel P.J., J. Org. Chem., 54,2542 (1989).
  • 5. Starling S.M., Vonwiller S.C. and Reek J.N.H., J. Org. Chem., 63,2262 (1998).
  • 6. Welniak M., Polish J. Chem.,72, 1021 (1998).
  • 7. Kropf H. in Houben-Weyl, 4th Ed., Thieme: Stuttgart, 1980, Vol. Vl/1a, p. 1216.
  • 8. Gosselin P., Joulain D., Laurin P. and Rouessac F., Tetrahedron Lett., 32, 3151 (1990).
  • 9. Dmitrov V., Eratovanov S,, Simova S. and Kostova K., Tetrahedron Lett., 6713 (1994).
  • 10. Dmitrov V., Simova S. and Kostova K., Tetrahedron, 52, 1699 (1996).
  • 11. Genov M., Kostova K. and Dmitrov V., Tetrahedron: Asymmetry, 8, 1869 (1997).
  • 12. Pallaud R. and Pleu J., C. R. Acad. Sc. Paris, 256C, 1479 (1967).
  • 13. Kozlov N.G., PopovaL.A. and NestrowG.V., Zh. Obsch. Khim., 56, 1562 (1986).
  • 14. Pretsch E., Clerk T., Seibl I. and Simon W., Tabellen zur Strukturaufklänmg organischer Verbindungen mit spektroskopischen Methoden, Berlin-Heilderberg-NY: Springer-Verlag 1981, p. H 190.
Typ dokumentu
Bibliografia
Identyfikator YADDA
bwmeta1.element.baztech-article-BUJ1-0020-0005
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