Evidence for oxacarbenium ion intermediates in the Lewis acid promoted cleavage of spirocyclic dioxanes

Journal of the Chemical Society - Perkin Transactions 1

Volumn , Issue 14, 1997, Pages 2033-2036

  Newitt, Lee A ^a   Steel, Patrick G ^a  

^a DURHAM UNIVERSITY   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33748978243     PISSN: 0300922X     EISSN: None     Source Type: Journal    
DOI: 10.1039/a701764b     Document Type: Article

References (12)

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2. A. Alexakis and P. Mangeney, Tetrahedron: Asymmetry, 1990, 477 and references cited therein.
3. S. E. Denmark and N. G. Almstead, J. Am. Chem. Soc., 1991, 113, 8089 and references cited therein.
4. I. Mori, K. Ishihara, L. A. Flippin, K. Nozaki, H. Yamamoto, P. A. Bartlett and C. H. Heathcock, J. Org. Chem., 1990, 55, 6107.
5. Y. Yamamoto, S. Nishii and J. Yamada, J. Am. Chem. Soc., 1986, 108, 7116.
6. (a) R. S. Smith and T. Sammakia, J. Org. Chem., 1992, 57; 2997;
7. (b) R. S. Smith and T. Sammakia, J. Am. Chem. Soc., 1992, 114, 10 998 and references cited therein.
8. For a review see T. Harada and A. Oku, Synlett, 1994, 2, 95.
9. It should be noted that there is a difference between acyclic, cyclic and spirocyclic acetals since Sammakia, employing specifically deuteriated acyclic acetals, has ruled out selective Lewis acid binding as the means of achieving asymmetric induction, see ref. 6(b).
10. Recently, whilst this manuscript was in preparation, the enantioselective cleavage of 1,3-dioxolanes was reported. M. Kinugasa, T. Harada and A. Oku, J. Org. Chem., 1996, 61, 6772. Interestingly the use of dioxolanes rather than dioxanes appears crucial.
11. The product alcohols do show evidence of strong intramolecular hydrogen bonding (no D exchange) which would be promoted by a Thorpe-Ingold effect.
12. D. D. Perrin and W. L. F. Armarego, Purification of Laboratory Chemicals, Pergamon Press, Oxford, 3rd edn., 1988.