Reactivity control via dihydrogen bonding: Diastereoselection in borohydride reductions of α-hydroxyketones [6]

Journal of the American Chemical Society

Volumn 121, Issue 37, 1999, Pages 8655-8656

  Gatling, Sterling C ^a   Jackson, James E ^a  

^a MICHIGAN STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BORANE DERIVATIVE; KETOL;

CHEMOREACTIVITY; DIASTEREOISOMER; HYDROGEN BOND; LETTER; MOLECULAR INTERACTION; REACTION ANALYSIS; REDUCTION; REGULATORY MECHANISM; STEREOCHEMISTRY;

EID: 0033595588     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991784n     Document Type: Letter

References (25)

1. (a) Lee, J. C.; Peris, E.; Rheingold, A. L.; Crabtree, R. H. J. Am. Chem. Soc. 1994, 116, 11014.
2. (b) Crabtree, R. H.; Siegbahn, P. E. M.; Eisenstein, O.; Rheingold, A. L.; Koetzle, T. F. Acc. Chem. Res. 1996, 29, 348.
3. (c) Qiang, L.; Hoffmann, R. J. Am. Chem. Soc. 1995, 117, 10108.
4. (d) Park, S.; Lough, A. J.; Morris, R. H. Inorg. Chem. 1996, 35, 3001.
5. (e) Alkota, I.; Elguero, J.; Concepcion, F.-F. J. Chem. Soc., Chem. Commun. 1996, 1633.
6. (f) Gelabert, R.; Moreno, M.; Lluch, J. M.; Lledos, A. Organometallics 1997, 16, 3805.
7. 2O: Huang, R.; Sharma, M.; Eckert, J.; Argyriou, D.; Sheldon, R.; Jackson, J. E. Manuscript in preparation.
8. (b) Sharma, M. Report to the Westinghouse Science Talent Search Committee, Fall 1994.
9. (c) Wilson, C.; Inman K.; Jackson, J. E. Manuscript in preparation.
10. (a) Custelcean, R.; Jackson, J. E. J. Am. Chem. Soc. 1998, 120, 12935.
11. (b) Custelcean, R.; Jackson, J. E. Angew. Chem., Int. Ed. Engl. 1999, 38, 1661.
12. Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902.
13. -, -2.9; 1, -68.0; vdW complex syn to -OH, -86.3; vdW complex anti to -OH, -81.5; TS syn to -OH, -81.8; TS anti to -OH, -78.3.
14. Substrates 2, 4, and 6-9 were purchased from Aldrich Chemical Co. and used without further purification. Compounds 1 and 3 were prepared via acyloin reactions of dimethyl succinate and dimethyl glutarate, respectively, following the literature procedure for preparation of 1 (see: Johnson, C. R. Organic Syntheses; Johnson, C. R., Ed.; John Wiley & Sons: New York, 1977; Vol. 57, pp 1-7). Compound 5 was obtained by treating its dimer (adipoin purchased from Aldrich) with dilute (5%) HCl. The product was extracted with dichloromethane, dried, and stripped of solvent.
15. In a typical experiment, 0.64 g (2.5 mmol) of solid tetrabutylammonium borohydride was added to a solution of ketone (2.5 mmol) in dichloromethane (10 mL), and the reaction vessel was vigorously shaken or stirred and then allowed to stand for 0.25-150 h with periodic monitoring by IR and/or NMR. Quenching with 20 mL of 3% hydrogen peroxide, followed by 10 mL of 10% sodium hydroxide, was followed by layer separation and extraction of the aqueous phase with three 30-raL portions of dichloromethane. The combined organic solutions were extracted with 20 mL of saturated sodium sulfite, dried over anhydrous sodium sulfate, and concentrated under reduced pressure (note, the diol products are very water soluble and therefore difficult to extract into the organic phase). The crude product was taken up in anhydrous diethyl ether, the insoluble tetrabutylammonium salts were removed by filtration, and the ether solvent was evaporated. Quantitative analysis was carried out by conventional trimethylsilylation/capillary gas chromatography.
16. - on the carbonyl carbon. See: Krishnan, K.; Chandrasekaran, J. Indian J. Chem. 1982, 21B, 595.
17. (a) Saksena, A. K.; Mangiaracina, P. Tetrahedron Lett. 1983, 24, 273.
18. (b) Evans, D. A.; Chapman, K. T. Tetrahedron Lett. 1986, 27, 5939.
19. (c) Gribble, G. W. Chem. Soc. Rev. 1998, 27, 395.
20. (a) Wuesthoff, M. T. Tetrahedron 1973, 29, 791.
21. (b) Wigfield, D. C. Tetrahedron 1979, 35, 449.
22. (c) Brown, H. C.; Krishnamurthy, S. Tetrahedron 1979, 35, 567.
23. (a) Wigfield, D. C.; Gowland, F. W. J. Org. Chem. 1977, 42, 1108.
24. (b) Pierre, J.-L.; Handel, H. Tetrahedron Lett. 1974, 2317.
25. The fluoride result, in which the stereopreference is actually reversed, suggests that it might be possible to use this strategy to intentionally disfavor hydroxylated sites.