Selective Reduction of Aliphatic Ketones and Aldehydes to Hydrocarbons with Sodium Cyanoborohydride and p-Toluenesulfonyl Hydrazide in Dimethylformamide-Sulfolane

Journal of the American Chemical Society

Volumn 93, Issue 7, 1971, Pages 1793-1794

  Hutchins, Robert O ^a   Maryanoff, Bruce E ^a   Milewski, Cynthia A ^a  

^a DREXEL UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001296483     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00736a044     Document Type: Letter

References (17)

1. A recent critical review containing 170 references concerning methods for deoxygenation of carbonyl compounds and a comparison of their effectiveness is provided by W. Reusch in “Reduction,” R. L. Augustine, Ed., Marcel Dekker, New York, N. Y., 1968, pp 171-211.
2. For the direct conversion of aromatic acids to hydrocarbons, see R. A. Benkeser, K. M. Foley, J. M. Gaul, and G. S. Li, J. Amer. Chem. Soc, 92, 3232 (1970).
3. A common indirect method of conversion of carbonyl derivatives, including esters and acids, involves lithium aluminum hydride reduction to an alcohol followed by conversion to the tosylate or halide and displacement using a metal hydride, usually lithium aluminum hydride [see, for example, L. S. Trevoy and W. G. Brown, J. Amer. Chem. Soc, 71, 1675 (1949);
4. G. Buchi, W. Hofheinz, and J. Paukstelis, J. Amer. Chem. Soc, 88, 4113 (1966)].
5. More recently, sodium borohydride in polar aprotic solvents has proven effective for selective conversion of the halides or tosylates to hydrocarbons; see R. O. Hutchins, D. Hoke, J. Keogh, and D. Koharski, Tetrahedron Lett., 3495 (1969);
6. H. M. Bell, C. W. Vanderslice, and A. Spehar, J. Org. Chem., 34, 3923 (1969);
7. E. J. Corey, H. A. Kirst, and J. A. Katzenellenbogen, J. Amer. Chem. Soc, 92, 6314 (1970).
8. Huang-Minlon, J. Amer. Chem. Soc, 70, 2802 (1948).
9. L. Caglioti, Tetrahedron, 22, 487 (1966);
10. L. Caglioti and P. Grasselli, Chem. Ind. (London), 153 (1964).
11. M. Fischer, Z. Pelah, D. H. Williams, and C. Djerassi, Chem. Ber., 98, 3236 (1965).
12. Caglioti (ref 4) reports concomitant reduction of acetoxy groups when steroidal ketone tosylhydrazones are deoxygenated with sodium borohydride in methanol and/or dioxane at reflux temperatures. Reduction of esters by borohydride in methanol has also been observed by others; see, for example, M. S. Brown and H. Rapoport, J. Org. Chem., 28, 3261 (1963).
13. Aromatic nitro groups also would probably not survive borohydride treatment in refluxing methanol or dioxane; see H. J. Shine and H. E. Mallory, J. Org. Chem., 27, 2390 (1962);
14. R. O. Hutchins, D. W. Lamson, L. Rua, C. Milewski, and B. Maryanoff, J. Org. Chem., in press.
15. R. F. Borch and H. Durst, J. Amer. Chem. Soc, 91, 3996 (1969), have recently reported an excellent procedure for the reductive animation of aldehydes and ketones using lithium cyanoborohydride and amines in acidic methanol. The success of the method depends on the relatively rapid reduction of imminium ions over carbonyls by cyanoborohydride and on the stability of the reagent toward acid.
16. See also M. M. Kreevoy and J. E. C. Hutchins, J. Amer. Chem. Soc, 91, 4330 (1969).
17. For other procedures used to convert β-keto esters to saturated esters, see R. M. Coates and J. E. Shaw, J. Org. Chem., 35, 2601 (1970), and references cited therein. These authors used a two-step procedure involving methoxymethylation followed by lithium-in-ammonia reduction to the esters in 23-61 % yields.