Stereoselective reduction of unsaturated 1,4-diketones. A practical route to chiral 1,4-diols

Tetrahedron Letters

Volumn 38, Issue 6, 1997, Pages 1091-1094

  Bach, Jordi ^a   Berenguer, Ramon ^a   Garcia, Jordi ^a   Loscertales, Teresa ^a   Manzanal, Judith ^a   Vilarrasa, Jaume ^a  

^a UNIVERSITY OF BARCELONA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANEDIOL DERIVATIVE;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; IN VITRO STUDY; REACTION ANALYSIS; REDUCTION; STEREOCHEMISTRY;

EID: 0031562081     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(96)02476-8     Document Type: Article

References (32)

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4. (d) Kim, M.-J.; Lee, I.S. Synlett 1993, 767.
5. 2. (a) Burk, M.J.; Feaster, J.E.; Harlow, R.L. Tetrahedron:Asymmetry 1991, 2, 569.
6. (b) Burk, M.J; Harper, T.G.P.; Kalberg, C.S. J. Am. Chem. Soc. 1995, 117, 4423, and references therein.
7. 3. (a) Mattson, A.; Öhrner, N.; Hult, K.; Norin, T. Tetrahedron:Asymmetry 1993, 4, 925.
8. (b) Kim, M.-J.; Lee, I.S. J. Org. Chem. 1993, 55, 6483.
9. (c) Nagai, H.; Morimoto, T.; Achiwa, K Synlett 1994, 289.
10. (d) Caron, G.; Kazlauskas, R.J. Tetrahedron:Asymmetry 1994, 5, 657. Also see ref. 1d.
11. 4. Ross, S.D.; Finkelstein, M.; Rudd, E.J. Anodic Oxidation; Academic Press: New York, 1975. Also see ref. 2a.
12. 5. For instance, (S,S)-hexane-2,5-diol has been prepared from parent hexane-2,5-dione by baker yeast reduction (Lieser, J.K. Synth. Commun. 1983, 765) and by asymmetric hydrosilylation catalysed by a chiral rhodium complex (Kuwano, R.; Sawamura, M.; Shirai, J.; Takahashi, M.; Ito, Y. Tetrahedron Lett. 1995, 36, 5239).
13. 5. For instance, (S,S)-hexane-2,5-diol has been prepared from parent hexane-2,5-dione by baker yeast reduction (Lieser, J.K. Synth. Commun. 1983, 765) and by asymmetric hydrosilylation catalysed by a chiral rhodium complex (Kuwano, R.; Sawamura, M.; Shirai, J.; Takahashi, M.; Ito, Y. Tetrahedron Lett. 1995, 36, 5239).
14. 6. Reduction of aromatic diketones with B-chlorodiisopinocampheylborane have recently been described: Ramachandran, P.V.; Chen, G.-M.; Lu, Z.-H.; Brown, H.C. Tetrahedron Lett. 1996, 37, 3795. Also see ref. 1c.
15. 7. For recent reviews, see: (a) Wallbaum, S.; Martens, J. Tetrahedron:Asymmetry 1992, 3, 1475.
16. (b) Deloux, L.; Srebnik, M. Chem. Rev. 1993, 93, 763.
17. 8. (a) Quallich, G.J.; Keavey, K.N.; Woodall, T.M. Tetrahedron Lett. 1995, 36, 4729.
18. (b) Chong et al. have also reported (ref. 1c) the oxazaborolidine-mediated reduction of 1,4-diphenylbutane-1,4-dione.
19. For related reductions of other diketones, see: (c) 1,1'-ferrocenediones: Schwink, L.; Knochel, P. Tetrahedron Lett. 1996, 37, 25;
20. (d) aromatic 1,2-diketones: Prasad, K.R.K., Joshi, N.N. J. Org. Chem. 1996, 61, 3888;
21. (e) nona-1,8-diyne-3,7-dione: Parker, K.A.; Ledeboer, M.W. J. Org. Chem. 1996,61, 3214.
22. 9. (a) Reduction of enones: Bach, J.; Berenguer, R.; Farràs, J.; Garcia, J.; Meseguer, J.; Vilarrasa, J., Tetrahedron:Asymmetry 1995, 6, 2683.
23. (b) Reduction of ynones: Bach, J.; Berenguer, R.; Garcia, J.; Loscertales, T.; Vilarrasa, J. Org. Chem., in press.
24. For related reductions, see: (c) Corey, E.J., Helal, C.J. Tetrahedron Lett. 1995, 36, 9153. Also see ref. 8e.
25. 10. Compounds 2a and 2b were easily obtained by oxidative opening of 2,5-dimethylfuran and 2,5-diethylfuran, respectively. For a review on the synthesis of 1,4-dicarbonyl compounds from furans, see: Piancatelli, G.; D'Auria, M.; D'Onofrio, F. Synthesis 1994, 867.
26. 2 (2 mmol) in THF reduces very fast one of the carbonyl groups of the first mmol of 2b (89% of ketol within 5 min) but much slower the second one (~22% of diol within 1 h). This fact agrees with the lower diastereoselectivity obtained in borane-mediated reductions of diketones 2 catalysed by 6 in relation to that expected from statistical arguments (assuming that both, the first and the second reduction, run independently and with similar facial selectivities to those noted for related unsaturated monoketones). Further details and additional experiments will be reported in the full paper.
27. 2, Pd/C, MeOH) of 2a and 2b, respectively.
28. 2 for 2 days at -20 °C (Gao, Y.; Hanson, R.M.; Klunder, J.M.; Ko, S.Y.; Masamune, H.; Sharpless, K.B. J. Am. Chem. Soc. 1987, 109, 5765). After work-up, recovered diol 7a showed a 99:1 dl:meso ratio and 99% e.e. (52% overall yield from diketone 2a).
29. 14. In general, catalytic hydrogenation (Pt/C, MeOH or AcOEt) of chiral diols 7 and 9 gives the corresponding saturated diols in good yields and negligible loss of optical purity.
30. 8 in pentane.
31. 16. Preparation of chiral 2-ene-1,4-diol based on organozinc chemistry has been reported: Vettel, S.; Knochel, P. Tetrahedron Lett. 1994, 35, 5849.
32. 4NF (Cox, D.P.; Terpinski, J.; Lawrynowicz, W. J. Org. Chem. 1984, 49, 3216) followed by oxidation (60% overall yield). As far as 3d is concerned, we obtained better overall yields by means of a stepwise process: (equation presented)