Oxazaborolidine-mediated reduction of prochiral 2-alkylidene cycloalkanones

Tetrahedron Asymmetry

Volumn 8, Issue 5, 1997, Pages 673-676

  Simpson, Alison F ^a   Szeto, Peter ^a   Lathbury, David C ^b   Gallagher, Timothy ^a  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

^b SB Pharmaceuticals   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANOL; CYCLOALKANOL DERIVATIVE;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; IN VITRO STUDY; METHODOLOGY; PRIORITY JOURNAL; REACTION ANALYSIS; REDUCTION;

EID: 0031053524     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(97)00034-7     Document Type: Article

References (28)

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2. (b) Singh, V. K. Synthesis, 1992, 605-617.
3. The electronic influence of remote substituents is important in oxazaborolidine-mediated reductions. (a) Corey, E. J.; Helal, C. J. Tetrahedron Lett. 1995, 36, 9153-9156.
4. (b) Helal, C. J.; Magriotis, P. A.; Corey, E. J. J. Am. Chem. Soc. 1996, 118, 10938-10939.
5. 4 modified by (-)-N-methylephedrine, see Iwasaki, G.; Sano, M.; Sodeoka, M.; Yoshida, K.; Shibasaki, M. J. Org. Chem. 1988, 53, 4864-4867.
6. (b) Use of yeast as reductant in the preparation of 2b (99% e.e.), see Fronza, G.; Fogliato, G.; Fuganti, C.; Lanati, S.; Rallo, R.; Servi, S. Tetrahedron Lett. 1995, 36, 123-124; Fronza, G.; Fogliato, G.; Fuganti, C.; Lanati, S.; Rallo, R.; Rigoni, R.; Servi, S. Tetrahedron 1995, 51, 10231-10240. Only the absolute stereochemistry of 2b has been established unambiguously.
7. (b) Use of yeast as reductant in the preparation of 2b (99% e.e.), see Fronza, G.; Fogliato, G.; Fuganti, C.; Lanati, S.; Rallo, R.; Servi, S. Tetrahedron Lett. 1995, 36, 123-124; Fronza, G.; Fogliato, G.; Fuganti, C.; Lanati, S.; Rallo, R.; Rigoni, R.; Servi, S. Tetrahedron 1995, 51, 10231-10240. Only the absolute stereochemistry of 2b has been established unambiguously.
8. (a) Corey, E. J.; Bakshi, R. K.; Shibati, S. J. Am. Chem. Soc. 1987, 109, 5551-5553.
9. (b) Corey, E. J.; Bakshi, R. K.; Shibati, S.; Chen, C. P.; Singh, V. K. J. Am. Chem. Soc. 1987, 109, 7925-7926.
10. (c) Corey, E. J.; Shibati, S.; Bakshi, R. K. J. Org. Chem. 1988, 53, 2861-2863. For synthetic applications of 3 see ref. 2a and for a review on the use of oxazaborolidines in asymmetric synthesis, see Wallbaum, S.; Martens, J. Tetrahedron: Asymmetry 1992, 3, 1475-1504.
11. (c) Corey, E. J.; Shibati, S.; Bakshi, R. K. J. Org. Chem. 1988, 53, 2861-2863. For synthetic applications of 3 see ref. 2a and for a review on the use of oxazaborolidines in asymmetric synthesis, see Wallbaum, S.; Martens, J. Tetrahedron: Asymmetry 1992, 3, 1475-1504.
12. Itsuno, S.; Sakurai, Y.; Ito, K.; Hirao, A.; Nakahama, S. Bull. Chem. Soc. Jpn. 1987, 60, 395-396.
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14. Mathre, D. J.; Jones, T. K.; Xavier, L. C.; Blacklock, T. J.; Reamer, R. A.; Mohan, J. J.; Turner Jones, E. T.; Hoogsteen, K.; Baum, M. W.; Grabowski, E. J. J. J. Org. Chem. 1991, 56, 751-762. Mathre, D. J.; Thompson, A. S.; Douglas, A. W.; Hoogsteen, K.; Carroll, J. D.; Corley, E. G.; Grabowski, E. J. J. J. Org. Chem. 1993, 58, 2880-2888.
15. For the preparation of enone substrates: 1a Phillips, A. P.; Mentha, J. J. Am. Chem. Soc. 1956, 78, 140-145;
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17. 1c Hückel, W.; Maier, M.; Jordan, E.; Seeger, W. Liebigs Ann. Chem. 1958, 616, 46-81, Varech, D.; Ouannes, C.; Jacques, J. Bull. Soc. Chim. Fr. 1965, 32, 1662-1669;
18. 1c Hückel, W.; Maier, M.; Jordan, E.; Seeger, W. Liebigs Ann. Chem. 1958, 616, 46-81, Varech, D.; Ouannes, C.; Jacques, J. Bull. Soc. Chim. Fr. 1965, 32, 1662-1669;
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20. Stockman, R. A.; Szeto, P.; Thompson, S. H. J.; Hadley, M. S.; Lathbury, D. C.; Gallagher, T. Synlett 1996, 853-855.
21. 2 (0.3 mL) at -20°C. After completion of reaction (1 to 1.5 h), cold methanol (3 mL) was added and the solution was then stirred for 1 h. Concentration in vacuo followed by rapid flash chromatography (90:10 hexane:EtOAc) gave allylic alcohols 2.
22. For the effect of temperature on the efficiency of oxazaborolidine reductions, see Stone, G. B. Tetrahedron: Asymmetry 1994, 5, 465-472. For further mechanistic studies, see Douglas, A. W.; Tschaen, D. M.; Reamer, R. A.; Shi, Y. J. Tetrahedron: Asymmetry 1996, 7, 1303-1308.
23. For the effect of temperature on the efficiency of oxazaborolidine reductions, see Stone, G. B. Tetrahedron: Asymmetry 1994, 5, 465-472. For further mechanistic studies, see Douglas, A. W.; Tschaen, D. M.; Reamer, R. A.; Shi, Y. J. Tetrahedron: Asymmetry 1996, 7, 1303-1308.
24. 3) see Dale, J. A., Dull, D. L.; Mosher, H. S. J. Org. Chem. 1969, 34, 2543-2549.
25. 4a (also Evans, D. A. Science 1988, 240, 420) and chair transition states have been suggested for the delivery of hydride. For computational studies on the possible role of a chair transition state see Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799-781; Linney, L. P.; Self, C. R.; Williams, I. H. J. Chem. Soc., Chem. Commun. 1994, 1651-2.
26. 4a (also Evans, D. A. Science 1988, 240, 420) and chair transition states have been suggested for the delivery of hydride. For computational studies on the possible role of a chair transition state see Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799-781; Linney, L. P.; Self, C. R.; Williams, I. H. J. Chem. Soc., Chem. Commun. 1994, 1651-2.
27. 4a (also Evans, D. A. Science 1988, 240, 420) and chair transition states have been suggested for the delivery of hydride. For computational studies on the possible role of a chair transition state see Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799-781; Linney, L. P.; Self, C. R.; Williams, I. H. J. Chem. Soc., Chem. Commun. 1994, 1651-2.
28. 3b, the other allylic alcohols described in this paper have not previously been described in enantiomerically enriched form. All new compounds have been fully characterised.