Role of cyclopropanes as activating groups during oxidation reactions with RuO4 generated in situ

Tetrahedron Letters

Volumn 37, Issue 14, 1996, Pages 2425-2428

  Coudret, Jean Luc ^a,b   Zöllner, Stephan ^b   Ravoo, Bart Jan ^a   Malara, Lionnel ^a   Hanisch, Christian ^a   Dörre, Klaus ^a   De Meijere, Armin ^b   Waegell, Bernard ^a  

^a AIX MARSEILLE UNIVERSITY   (France)

^b UNIVERSITY OF GÖTTINGEN   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPROPANE DERIVATIVE; KETONE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; TECHNIQUE;

EID: 17144472368     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00325-5     Document Type: Article

References (28)

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11. 4 see: Hugel, G.; Lods, L.; Meltor, J. M.; Ourisson, G. Bull. Soc. Chim. Fr. 1965, 2894-2902.
12. 4 see: Hugel, G.; Lods, L.; Meltor, J. M.; Ourisson, G. Bull. Soc. Chim. Fr. 1965, 2894-2902.
13. Zöllner, S. Dissertation, Universität Hamburg, 1991.
14. Compound 3 has been prepared by cyclopropanation of 2-methylenenorbomane using the Simmons-Smith reagent, applying the general procedure described by: Denis, J. M.; Girard, C.; Conia, J. M. Synthesis 1972, 549-551.
15. 3, see Kraus, W.; Klein, G.; Sadlo, H.; Rothenwöhrer, W. Synthesis 1972, 485-487.
16. 2 according to: Binger, P. Angew. Chem. 1972, 84, 352; Angew. Chem. Int. Ed. Engl. 1972, 11, 309.
17. 2 according to: Binger, P. Angew. Chem. 1972, 84, 352; Angew. Chem. Int. Ed. Engl. 1972, 11, 309.
18. -1), Bowry, V. W.; Lusztyk, J.; Ingold, K. U. J. Am. Chem. Soc. 1991, 113, 5687-5698.
19. In the rigid skeletons 1 and 3 the bridgehead C-H orbitals are perpendicular to the cyclopropyl Walsh Orbitals, hence no stabilisation of a developing positive charge on the bridgehead would be possible. The situation is different in the case of compound 5 with an interorbital angle between the bridgehead C-H and the adjacent cyclopropyl group of about 60°. In such cases a significant stabilisation of bridgehead carbocations has been observed (cf. de Meijere, A.; Schallner, O.; Weitemeyer, C.; Spielmann, W. Chem. Ber. 1979, 112, 908) and hence such positions could be rapidly hydroxylated with ozone on silica gel (cf. Zarth, M.; de Meijere, A. Chem. Ber. 1985, 115, 2429).
20. In the rigid skeletons 1 and 3 the bridgehead C-H orbitals are perpendicular to the cyclopropyl Walsh Orbitals, hence no stabilisation of a developing positive charge on the bridgehead would be possible. The situation is different in the case of compound 5 with an interorbital angle between the bridgehead C-H and the adjacent cyclopropyl group of about 60°. In such cases a significant stabilisation of bridgehead carbocations has been observed (cf. de Meijere, A.; Schallner, O.; Weitemeyer, C.; Spielmann, W. Chem. Ber. 1979, 112, 908) and hence such positions could be rapidly hydroxylated with ozone on silica gel (cf. Zarth, M.; de Meijere, A. Chem. Ber. 1985, 115, 2429).
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26. Bicyclopentane 20 was prepared according to Gassman, P. G.; Mansfield, K. T. Org. Synth., Coll. Vol. V, Baumgarten, H. E. Ed., Wiley, New York, 1973, 96-101.
27. 4 bond. Cf. Preuß, T.; Proksch, E.; de Meijere, A. Tetrahedron Lett. 1974, 833-836.
28. B. Akermark, R. I. T. Stockholm, personal communication.