Selective Reductions. XV. Reaction of Diborane in Tetrahydrofuran with Selected Organic Compounds Containing Representative Functional Groups

Journal of the American Chemical Society

Volumn 92, Issue 6, 1970, Pages 1637-1646

  Brown, Herbert C ^a   Heim, Peter ^a   Yoon, Nung Min ^a  

^a PURDUE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0002760231     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00709a037     Document Type: Article

References (44)

1. H. C. Brown, “Hydroboration,” W. A. Benjamin, Inc., New York, N. Y., 1962.
2. H. C. Brown, Accad. Naz. Lincei, 73 (1968).
3. H. C. Brown, Accounts Chem. Res., 2, 65 (1969).
4. H. C. Brown, H. I. Schlesinger, and A. B. Burg, J. Amer. Chem. Soc., 61, 673 (1939).
5. H. C. Brown and B. C. Subba Rao, J. Amer. Chem. Soc., 82, 681 (1960).
6. H. C. Brown and W. Korytnyk, J. Amer. Chem. Soc., 82, 3866 (1960).
7. H. C. Brown and N. M. Yoon, J. Amer. Chem. Soc., 88, 1464 (1966).
8. H. C. Brown, P. M. Weissman, and N. M. Yoon, J. Amer. Chem. Soc., 88, 1458 (1966).
9. H. C. Brown and P. M. Weissman, J. Amer. Chem. Soc., 87, 5614 (1965).
10. H. C. Brown and P. M. Weissman, Israel J. Chem., 1, 430 (1963).
11. H. O. House, “Modern Synthetic Reactions,” W. A. Benjamin, Inc., New York, N. Y., 1965, Chapter 7.
12. H. C. Brown, E. J. Mead, and B. C. Subba Rao, J. Amer. Chem. Soc., 77, 6209 (1955).
13. Hydrogenolysis of alcohols, using “mixed hydrides” have been extensively studied. See J. H. Brewster and H. O. Bayer, J. Org. Chem., 29, 105 (1964), and references therein.
14. E. Breuer, Tetrahedron Lett., 1849 (1967).
15. H. C. Brown and H. R. Deck, J. Amer. Chem. Soc., 87, 5620 (1965).
16. Cinnamyl alcohol, when allowed to react with diborane, gave, along with expected glycols, large amounts of monoalcohols. See K. Kratzl and P. Claus, Monatsh. Chem., 94, 1140 (1963).
17. However, by using disiamylborane to reduce the carbonyl groups, followed by diborane for hydroboration, the elimination was largely avoided, giving the glycol (after oxidation) in yields as high as 92%: H. C. Brown and R. M. Gallivan, Jr., J. Amer. Chem. Soc., 90, 2906 (1968).
18. It has been reported that anthraquinone is readily reduced at room temperature by sodium borohydride in pure diglyme to anthra-hydroquinone: D. S. Bapat, B. C. Subba Rao, M. K. Unni, and K. Venkataraman, Tetrahedron Lett., No. 5, 15 (1960). This is in apparent contradiction to an earlier report.”
19. G. S. Panson and C. E. Weill, J. Org. Chem., 22, 120 (1957).
20. S. L. Ioffe, V. A. Jartakovskii, and S. S. Novikov, Izv. Akad. Nauk SSSR, Ser. Khim., 622 (1964).
21. H. C. Brown and W. J. Wallace, Abstracts, 142nd National Meeting of the American Chemical Society, Atlantic City, N. J., 1962, No. 9N;
22. W. J. Wallace, Dissertation Abstr., 22, 425 (1961).
23. We previously suggested a cis-elimination mechanism for a (3-acetoxyorganoborane. See H. C. Brown and O. J. Cope J. Amer. Chem. Soc., 86, 1801 (1964), and ref 15.
24. In this connection it is interesting to note that the three isomeric butyl esters of 5β-cholanic acid were reduced to the corresponding ethers with diborane in the presence of a large excess of boron trifluoride; G. R. Petit and D. M. Piatak, J. Org. Chem., 27, 2127 (1962).
25. It has been reported that in 12 days reaction at room temperature, 41 % of 2-phenylethanol, 1 % of 1-phenylethanol, and 24% of 2-n-butoxy-2-phenylethanol were obtained. See D. J. Pasto, C. C. Cumbo, and J. Hickman, J. Amer. Chem. Soc., 88, 2201 (1966).
26. H. C. Brown and N. M. Yoon, J. Amer. Chem. Soc., 90, 2686 (1968).
27. H. C. Brown and N. M. Yoon, Chem. Commun., 1549 (1968).
28. H. C. Brown and P. Heim, J. Amer. Chem. Soc., 86, 3566 (1964). A detailed study of such reductions has been completed and will shortly be reported.
29. Diborane has been successfully utilized for the reduction of N-substituted fluoroacetamide derivatives to the corresponding fluoro-ethylamines in cases where lithium aluminum hydride and lithium aluminum hydride-aluminum chloride cause hydrogenolysis of the fluorine-carbon bond: Z. B. Papanastassiou and R. J. Bruni, J. Org. Chem., 29, 2870 (1964).
30. see also E. R. Bissell and M. Finger, J. Org. Chem., 24, 1256 (1959), and
31. G. R. Pettit, S. K. Gupta, and P. A. Whitehouse, J. Med. Chem., 10, 692 (1967).
32. The successful application of diborane for the reduction of the tertiary amide group in the presence of (i) the carbamate moiety and (ii) the ester moiety has been achieved: W. V. Curran and R. B. Angier, J. Org. Chem., 31, 3867 (1966).
33. M. J. Kornet, P. A. Thio, and S. I. Tan, J. Org. Chem., 33, 3637 (1968).
34. Finally, it has proven possile to reduce 1,2-diacylhydrazines to 1,2-dialkylhydrazines, so that the reduction of the tertiary amide grouping without rupture of the nitrogen-nitrogen hydrazine bond is demonstrated: H. Feuer and F. Brown, Jr., J. Org. Chem., in press.
35. Alkylamine-borane reduces acyl halides, aldehydes, and ketones, but is inert to esters, carboxylic acids, and amides; see H. Noth and H. Beyer, Ber., 93, 1078 (1960).
36. H. J. Emeleus and K. Wade, J. Chem. Soc., 2614 (1960).
37. H. Feuer, R. S. Bartlett, B. F. Vincent, Jr., and R. S. Anderson, J. Org. Chem., 30, 2880 (1965).
38. H. Feuer and D. M. Braustein, J. Org. Chem., 34, 2024 (1969).
39. H. Feuer, B. F. Vincent, Jr., and R. S. Bartlett, J. Org. Chem., 30, 2877 (1965).
40. S. L. Ioffe, V. A. Tartakovskii, A. A. Medvedeva, and S. S. Novikov, Izc. Akad. Nauk SSSR, Ser. Khim., 1537 (1964).
41. H. Feuer and D. M. Braustein, J. Org. Chem., 34, 1817 (1969).
42. H. C. Brown, P. Heim, and N. M. Yoon, manuscript in preparation.
43. H. C. Brown, D. B. Bigley, S. K. Arora, and N. M. Yoon, manuscript in preparation.
44. G. Zweifel and H. C. Brown, Org. Reactions, 13, 1 (1963).