Bulletin of the Korean Chemical Society

  • 제15권10호
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  • Pages.881-888
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  • 1994
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Reaction of Sodium Tris(diethylamino)aluminum Hydride with Selected Organic Compounds Containing Representative Functional Groups

  • 발행 : 1994.10.20
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초록

The approximate rates and stoichiometry of the reaction of excess sodium tris(diethylamino)aluminum hydride (ST-DEA) with selected organic compounds containing representative functional groups under standardized conditions(tetrahydrofuran, $0{\circ}$) were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The reducing ability of STDEA was also compared with those of the parent sodium aluminum hydride (SAH) and lithium tris(diethylamino)aluminum hydride (LTDEA). The reagent appears to be milder than LTDEA. Nevertheless, the reducing action of STDEA is very similar to that observed previously for LTDEA, as is the case of the corresponding parent sodium and lithium aluminum hydrides. STDEA shows a unique reducing characteristics. Thus, benzyl alcohol, phenol and 1-hexanol evolved hydrogen slowly, whereas 3-hexanol and 3-ethyl-3-pentanol, secondary and tertiary alcohols, were essentially inert to STDEA. Primary amine, such as n-hexylamine, evolved only 1 equivalent of hydrogen slowly. On the other hand, thiols examined were absolutely stable. STDEA reduced aidehydes and ketones rapidly to the corresponding alcohols. The stereoselectivity in the reduction of cyclic ketones by STDEA was similar to that by LTDEA. Quinones, such as p-benzoquinone and anthraquinone, were reduced to the corresponding 1,4-dihydroxycyclohexadienes without evolution of hydrogen. Carboxylic acids and anhydrides were reduced very slowly, whereas acid chlorides were reduced to the corresponding alcohols readily. Esters and epoxides were also reduced readily. Primary carboxamides consumed hydrides for reduction slowly with concurrent hydrogen evolution, but tertiary amides were readily reduced to the corresponding tertiary amines. The rate of reduction of aromatic nitriles was much faster than that of aliphatic nitriles. Nitrogen compounds examined were also reduced slowly. Finally, disulfide, sulfoxide, sulfone, and cyclohexyl tosylate were readily reduced without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent: like LTDEA, STDEA converted ester and primary carboxamides to the corresponding aldehydes in good yields. Furthermore, the reagent reduced aromatic nitriles to the corresponding aldehydes chemoselectively in the presence of aliphatic nitriles. Consequently, STDEA can replace LTDEA effectively, with a higher selectivity, in most organic reductions.

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참고문헌

  1. Bull. Korean Chem. Soc. v.14 Cha, J. S.;Lee, J. C.
  2. J. Am. Chem. Soc. v.88 Brown, H. C.;Weissman, P. M.;Yoon, N. M.
  3. Tetrahedron Zakharkin, L. I.;Maslin, D. N.;Gavrilenko, V. V.
  4. Bull. Korean Chem. Soc. v.13 Cha, J. S.;Kim, J. M.;Jeoung, M. K.;Lee, K. D.
  5. Organic Synthesis via Boranes Brown, H. C.;Kramer, G. W.;Midland, M. M.
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  8. Org. Prep. Proced. Int. v.26 Cha, J. S.;Jeong, M. K.;Kim, J. M.;Kwon, O. O.;Kim, E. J.;Cha, J. S.;Jeoung, M. K.;Kim, J. M.;Kwon, O. O.;Lee, J. C.
  9. Bull. Korean Chem. Soc. v.13 Cha, J. S.;Lee, S. E
  10. Tetrahedron Lett. v.13 Cha, J. S.;Lee, S. E.;Lee, H. S.;Kim, J. M.;Kwon, O. O.;Min, S. J.
  11. Tetrahedron Lett. v.32 Cha, J. S.;Lee, J. C.;Lee, S. E.;Kim, J. M.;Kwon, O. O.;Lee, H. S.;Min, S. J.
  12. Org. Prep. Proced. Int. v.247 Cha, J. S.;Lee, J. C.;Lee, S. E.;Lee, H. S.;Cha, J. S.;Min, S. J.;Lee, J. C.;Lee, H. S.;Lee, S. E.
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피인용 문헌

  1. Thirty Six Years of Research on the Selective Reduction and Hydroboration vol.32, pp.6, 1994, https://doi.org/10.5012/bkcs.2011.32.6.1808
  2. Some Recommended Procedures for Conversion of Carboxylic Acid and Its Derivatives to Aldehydes by Metal Hydride Reductions vol.5, pp.2, 2012, https://doi.org/10.13160/ricns.2012.5.2.084