Vanadyl(IV) acetylacetonate

Vanadyl(IV) acetylacetonate

22 October, 2015 / by / in Reactions
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  • Generality
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  • General Characteristics

Vanadyl acetylacetonate (VO(acac)2) is used as a catalyst for epoxidation of allylic alcohols (with the use of tert-butyl hydroperoxide as the re-oxidant).

The directing effect of the hydroxyl group within the substrate allows for highly diastereoselective epoxidation of olefins.

  • General References

  • Indictor, I.; Brill, W. F. J. Org. Chem. 1965, 30, 2074. DOI: 10.1021/jo01017a520
  • Sharpless, K. B.; Michaelson, R. C. J. Am. Chem. Soc. 1973, 95, 6136. DOI: 10.1021/ja00799a061
  • Tanaka,S.; Yamamoto, H.; Nozaki, H.; Sharpless, K. B.; Michaelson, R. C.; Cutting, J. D. J. Am. Chem. Soc. 1974, 96, 5254. DOI: 10.1021/ja00823a042
  • Chong, A. O.; Sharpless, K. B. J. Org. Chem. 1977, 42, 1587. DOI: 10.1021/jo00429a024
  • Michaelson, R. C.; Palermo, R. E.; Sharpless, K. B. J. Am. Chem. Soc. 1977, 99, 1990. DOI: 10.1021/ja00448a059
  • Itoh, T.; Jitsukawa, K.; Kaneda, K.; Teranishi, S. J. Am. Chem. Soc. 1979, 101, 159. DOI: 10.1021/ja00495a027

<reviews>

  • Sharpless, K. B.; Verhoeven, T. R. Aldrichimica Acta 1979, 12, 63.
  • Butler, A.; Clagur, M.; Meister, G. E. Chem. Rev. 1994, 94, 625. DOI: 10.1021/cr00027a004
  • Hirao, T. Chem. Rev. 1997, 97, 2707. DOI: 10.1021/cr960014g

<selectivity>

  • Reaction MechanismVOacac_2

The order of reactivity is: allylic alcohols > homoallylic alcohols > simple alkenes.

VOacac_6

  • Examples

An application in the total synthesis of pectenotoxins.[1] VOacac_3

Selective epoxidation during the synthesis of anisatin.[2] VOacac_4

Synthesis of fumagillol[3]: The epoxidation of homoallylic alcohols is also possible for certain substrates meeting geometrical requirements.

VOacac_5

  • Experimental Procedure

  • Experimental Tips

  • References

  1. Evans, D. A.; Rajapakse, H. A.; Stenkamp, D. Angew. Chem. Int. Ed. 2002, 41, 4569. [abstract]
  2. Ogura, A.; Yamada, K.; Yokoshima, S.; Fukuyama, T. Org. Lett. 2012, 14, 1632. DOI: 10.1021/ol300390k
  3. (a) Vosburg, D. A.; Weiler, S.; Sorensen, E. J. Angew. Chem. Int. Ed. 1999, 38, 971. [abstract] (b) Vosburg, D. A.; Weiler, S.; Sorensen, E. J. Chirality 2003, 15, 156. DOI: 10.1002/chir.10181

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