Efficient and convergent stereocontrolled spiroannulation of ketones

Tetrahedron Letters

Volumn 44, Issue 16, 2003, Pages 3333-3336

  Markó, István E ^a   Vanherck, Jean Christophe ^a   Ates, Ali ^a   Tinant, Bernard ^b   Declercq, Jean Paul ^b  

^a UNIVERSITÉ CATHOLIQUE DE LOUVAIN   (Belgium)

^b NONE

Author keywords

Alkylation; Annulation; Orthoesters; Spirobicycle; Stereocontrol

Indexed keywords

ACETAL DERIVATIVE; KETONE DERIVATIVE;

ARTICLE; BIOTRANSFORMATION; CYCLIZATION; DIASTEREOISOMER; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; X RAY DIFFRACTION;

EID: 0037436954     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(03)00573-2     Document Type: Article

References (22)

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4. Markó I.E., Ates A. Synlett. 1999;1033.
5. For the elegant development of related orthoesters as cyclopentannulation reagents, see: (a) Ding, P.; Ghosez, L. Tetrahedron 2002, 58, 1565; (b) Huart, C.; Ghosez, L. Angew. Chem., Int. Ed. Engl. 1997, 36, 634. For the use of related acetals, see: Lee, T. V.; Boucher, R. J.; Porter, J. R.; Taylor, D. A. Tetrahedron 1988, 44, 4233.
6. For the elegant development of related orthoesters as cyclopentannulation reagents, see: (a) Ding, P.; Ghosez, L. Tetrahedron 2002, 58, 1565; (b) Huart, C.; Ghosez, L. Angew. Chem., Int. Ed. Engl. 1997, 36, 634. For the use of related acetals, see: Lee, T. V.; Boucher, R. J.; Porter, J. R.; Taylor, D. A. Tetrahedron 1988, 44, 4233.
7. For the elegant development of related orthoesters as cyclopentannulation reagents, see: (a) Ding, P.; Ghosez, L. Tetrahedron 2002, 58, 1565; (b) Huart, C.; Ghosez, L. Angew. Chem., Int. Ed. Engl. 1997, 36, 634. For the use of related acetals, see: Lee, T. V.; Boucher, R. J.; Porter, J. R.; Taylor, D. A. Tetrahedron 1988, 44, 4233.
8. 2, see: (a) Krief, A.; Laval, A.-M. Chem. Rev. 1999, 99, 745; (b) Molander, G. A. Chem. Rev. 1992, 92, 29; (c) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573.
9. 2, see: (a) Krief, A.; Laval, A.-M. Chem. Rev. 1999, 99, 745; (b) Molander, G. A. Chem. Rev. 1992, 92, 29; (c) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573.
10. 2, see: (a) Krief, A.; Laval, A.-M. Chem. Rev. 1999, 99, 745; (b) Molander, G. A. Chem. Rev. 1992, 92, 29; (c) Kagan, H. B.; Namy, J. L. Tetrahedron 1986, 42, 6573.
11. Repeating the reaction under identical conditions but adding small aliquots of water indeed led to some of the spiro derivative 6. However, the results were irreproducible from one experiment to another.
12. tBuOK, see: Williard, P. G.; MacEwan, G. J. J. Am. Chem. Soc. 1989, 111, 7671.
13. tBuOK, see: Williard, P. G.; MacEwan, G. J. J. Am. Chem. Soc. 1989, 111, 7671.
14. tBuOK, see: Williard, P. G.; MacEwan, G. J. J. Am. Chem. Soc. 1989, 111, 7671.
15. tBuOK, see: Williard, P. G.; MacEwan, G. J. J. Am. Chem. Soc. 1989, 111, 7671.
16. 3, Z=4. 5239 reflections were collected with a MAR image plate using monochromatized MoKα radiation (λ=0.71069 Å). The structure was solved and refined with SHELXS and SHELXL-97. (Sheldrick, G. M. (1997) University of Göttingen, Germany). The R indices converge to 0.0627 for 2636 observed reflections and to 0.0746 for all 3241 independent data.
17. Indeed, the iodo-substituted β-keto-ketals are obtained by condensation between the corresponding silyl enol ethers and the iodine-containing orthoester 2. This annulating agent is, in turn, generated by Finkelstein exchange from the initially prepared chloro-derivative (Ref. 2).
18. Hoffmann R.W. Chem. Rev. 89:1989;1841.
19. Boeckman R.K. Jr. J. Am. Chem. Soc. 95:1973;6867.
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21. For an alternative explanation, see: Asaoka M., Takenouchi K., Takei H. Chem. Lett. 1988;1225.
22. 3: C, 68.55; H, 8.63. Found: C, 68.29; H, 8.53.