DOI QR코드

DOI QR Code

Selective Reduction of Organic Compounds with Al-Trifluoromethanesulfonyldiisobutylalane. Comparison of Its Reactivity with Al-Methanesulfonyldiisobutylalane

  • Received : 2010.11.01
  • Accepted : 2010.11.15
  • Published : 2011.01.20

Abstract

The new MPV type reagent, Al-trifluoromethanesulfonyldiisobutylalane ($DIBAO_3SCF_3$), has been prepared and its reducing characteristics in the reduction of selected organic compounds containing representative functional groups have been examined, and compared its reactivity with that of Al-methanesulfonyldiisobutylalane ($DIBAO_3SCH_3$) in order to understand the fluorine-substituent effect on its reactivity. In general, the reactivity of $DIBAO_3SCF_3$ appears to be much higher than that of $DIBAO_3SCH_3$, apparently due to the acidity increase by the electron-withdrawing fluorine-substituent. The reagent reduced aldehydes and ketones readily, but showed a perfect selectivity in the reduction of $\alpha,\beta$-unsaturated aldehydes and ketones to produce the corresponding allylic alcohols in an absolutely 100% purity. In addition, the reagent achieved the regioselective cleavage of phenyl- or/and alkyl-substituted epoxides to the less substituted alcohols in a perfect regioselectivity. Moreover, the reagent also showed an high stereoselectivity in the reduction of substituted cycloalkanones to produce the thermodynamically more stable alcohol epimers exclusively.

Keywords

References

  1. Cha, J. S.; Yi, J. E. J. Incl. Phenom. Macro. 2009, 65, 15. https://doi.org/10.1007/s10847-009-9629-3
  2. Cha, J. S.; Park, S. J. Bull. Korean Chem. Soc. 2009, 30, 2823. https://doi.org/10.5012/bkcs.2009.30.11.2823
  3. Cha, J. S.; Park, S. J. Bull. Korean Chem. Soc. 2010, 31, 2135 https://doi.org/10.5012/bkcs.2010.31.8.2135
  4. Cha, J. S.; Noh, M. Bull. Korean Chem. Soc. 2010, 31, 840. https://doi.org/10.5012/bkcs.2010.31.04.840
  5. Brown, H. C.; Yoon, N, M. Chem. Commun. 1968, 1549.
  6. Hutchins, R. O.; Taffer, I. M.; Burgoyne, W. J. Org. Chem. 1981, 46, 5214. https://doi.org/10.1021/jo00338a031
  7. Yoon, N. M.; Kim, K. E. J. Org. Chem. 1987, 52, 5564. https://doi.org/10.1021/jo00234a011
  8. Cha, J. S.; Park, J. H. Bull. Korean Chem. Soc. 2002, 23, 1377. https://doi.org/10.5012/bkcs.2002.23.10.1377
  9. Cha, J. S.; Park, S. J.; Yu, S. J.; Kim, S. K.; Kwon, O. O. Bull. Korean Chem. Soc. 2008, 29, 301. https://doi.org/10.5012/bkcs.2008.29.2.301
  10. Cha, J. S. Org. Proc. Res. Devel. 2006, 10, 1032. https://doi.org/10.1021/op068002c
  11. Bull. Korean Chem. Soc. 2007, 28, 2162. https://doi.org/10.5012/bkcs.2007.28.12.2162
  12. Cha, J. S.; Kwon, O. O. J. Org. Chem. 1997, 62, 3019. https://doi.org/10.1021/jo970083a

Cited by

  1. Thirty Six Years of Research on the Selective Reduction and Hydroboration vol.32, pp.6, 2011, https://doi.org/10.5012/bkcs.2011.32.6.1808
  2. ChemInform Abstract: Selective Reduction of Organic Compounds with Al-Trifluoromethanesulfonyldiisobutylalane. Comparison of Its Reactivity with Al-Methanesulfonyldiisobutylalane. vol.42, pp.22, 2011, https://doi.org/10.1002/chin.201122033
  3. Regiospecific Ring-Opening of Unsymmetrical Epoxides to the Corresponding Less Substituted Alcohols by Newly-Devised Meerwein-Ponndorf-Verley Type Reagents vol.5, pp.2, 2012, https://doi.org/10.13160/ricns.2012.5.2.091
  4. Relative Reactivity of Various Al-substituted-dialkylalans in Reduction of Carbonyl Compounds: A Theoretical Study on Substituent Effect vol.34, pp.8, 2013, https://doi.org/10.5012/bkcs.2013.34.8.2335
  5. The Stereoselective Reductions of Ketones to the Most Thermodynamically Stable Alcohols Using Lithium and Hydrated Salts of Common Transition Metals vol.80, pp.16, 2015, https://doi.org/10.1021/acs.joc.5b01232