β-Butyrolactone as a chiral building block in organic synthesis: A convenient synthesis of MK-0507 keto sulfone

Tetrahedron Asymmetry

Volumn 7, Issue 9, 1996, Pages 2721-2724

  Tempkin, Orin ^a,b   Blacklock, Thomas J ^a,b   Burke, J Andrew ^a   Anastasia, Maria ^a,c  

^a Merck Mfg Division P O Box 2000   (United States)

^b Sandoz Pharma Ltd   (Switzerland)

^c Amersham Biosciences   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONATE DEHYDRATASE INHIBITOR; DORZOLAMIDE; GAMMA BUTYROLACTONE;

ARTICLE; CHEMICAL MODIFICATION; CHIRALITY; DRUG SYNTHESIS; ENANTIOMER; NUCLEAR MAGNETIC RESONANCE; PRIORITY JOURNAL; REACTION ANALYSIS;

EID: 0030248668     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/0957-4166(96)00350-3     Document Type: Article

References (20)

1. 1. Kaufman, P. L.; Robin, A. L.; Weinreb, R. N.; Crawford, K.; Shaw, B. Drugs 1991, 47, 514.
2. 2. Blacklock, T. J.; Sohar, P.; Butcher, J. W.; Lamanec, T.; Grabowski, E. J. J. J. Org. Chem. 1993, 58, 1672.
3. 3. (a) Breitschuh, R.; Seebach, D. Synthesis 1992, 83.
4. (b) Breitschuh, R.; Seebach, D. Synthesis 1992, 1170.
5. 4. Blacklock, T. J.; Shinkai, I. U.S. Patent 4 968 815, 1990.
6. 5. (a) Ohta, T.; Miyake, T.; Takaya, H. J. Chem. Soc., Chem. Commun. 1992, 1725.
7. (b) Takaya, H.; Ohta, T.; Kumobayashi, H. U.S. Patent 5 306 834, 1994.
8. (c) Ohta, T.; Miyake, T.; Seido, N.; Kumobayashi, H.; Takaya, H. J. Org. Chem. 1995, 60, 357.
9. 6. The ee of the β-butyrolactone was determined by chiral GC analysis. Konig, W.A., Krebber, R., Mishnic, P. J. High Resolut. Chromatogr. 1989, 12(11) , 732-738.
10. 7. The presence of THF is deleterious in the TFAA-mediated cyclization step.
11. 3. The organic layer was then analyzed.
12. 9. The oxidation in this case does not require sodium tungstate, an additive described in the 1993 procedure. This modification was developed by Dr. D. J. Mathre of Merck Process Research.
13. 14, using the same Chromatographic parameters as those for the keto sulfone assay except that the detector was operated at 240 nm. The retention times for the enantiomers were 50.2 min and 61.3 min. The amount of the hydroxy sulfone loaded onto the column should not exceed 2.0 μg to obtain satisfactory resolution.
14. 11. For the preparation of the Ru(II)-BINAP catalyst, see: King, S. A.; Thompson, A. S.; King, A. O.; Verhoeven, T. R. J. Org. Chem. 1992, 57, 6689.
15. 3(aq).
16. 13. Optically active β-butyrolactone has previously been prepared by the resolution and lactonization of 3-bromobutyric acid: Shelton, J. R.; Lando, J. B.; Agostini, D. E. J. Polym. Sci., Part B 1971, 9, 173. Seebach described a synthesis in 25% yield of the (S)-isomer of the lactone, via pyrolysis of an orthoester derivative of (R)-3-hydroxybutyric acid: Breitschuh, R.; Seebach, D. Chimia 1990, 44, 216 and references therein. Lenz et al. also recently published a five-step synthesis of the (S)-enantiomer (>97% ee) starting from poly[(R)-β-hydroxybutyrate] (PHB): Zhang, Y.; Gross, R. A.; Lenz, R. W. Macromolecules 1990, 23, 3206.
17. 13. Optically active β-butyrolactone has previously been prepared by the resolution and lactonization of 3-bromobutyric acid: Shelton, J. R.; Lando, J. B.; Agostini, D. E. J. Polym. Sci., Part B 1971, 9, 173. Seebach described a synthesis in 25% yield of the (S)-isomer of the lactone, via pyrolysis of an orthoester derivative of (R)-3-hydroxybutyric acid: Breitschuh, R.; Seebach, D. Chimia 1990, 44, 216 and references therein. Lenz et al. also recently published a five-step synthesis of the (S)-enantiomer (>97% ee) starting from poly[(R)-β-hydroxybutyrate] (PHB): Zhang, Y.; Gross, R. A.; Lenz, R. W. Macromolecules 1990, 23, 3206.
18. 13. Optically active β-butyrolactone has previously been prepared by the resolution and lactonization of 3-bromobutyric acid: Shelton, J. R.; Lando, J. B.; Agostini, D. E. J. Polym. Sci., Part B 1971, 9, 173. Seebach described a synthesis in 25% yield of the (S)-isomer of the lactone, via pyrolysis of an orthoester derivative of (R)-3-hydroxybutyric acid: Breitschuh, R.; Seebach, D. Chimia 1990, 44, 216 and references therein. Lenz et al. also recently published a five-step synthesis of the (S)-enantiomer (>97% ee) starting from poly[(R)-β-hydroxybutyrate] (PHB): Zhang, Y.; Gross, R. A.; Lenz, R. W. Macromolecules 1990, 23, 3206.
19. 4 in EtOH. The hydroxy sulfones may be epimerized to a mixture favoring the trans isomer using conditions described in reference 2. We are seeking new methods to selectively convert 1 to the trans hydroxy sulfone 6b which is desired for the next step. (equation presented)
20. 15. The synthetic and environmental significance of "one-pot" reactions has recently been reviewed: Hall, N. Science 1994, 266, 32.