Dess–Martin Periodinane

Chemfiles Volume 5 Article 1

Dess–Martin Periodinane (DMP) is among the most widely used reagents for the mild oxidation of alcohols to aldehydes and ketones.1 The neutral conditions of the oxidation reaction make it a suitable choice in syntheses of sensitive, functionally complex intermediates. When used in hydrophilic ionic liquids, DMP oxidations proceed even faster than in conventional solvents.2 Other advantages such as selectivity, avoiding the use of toxic (i.e. chromium-based) chemicals, using stoichiometric amounts of reagent, and ease of work-up make the Dess–Martin periodinane a reliable and easy-to-use oxidizer in organic synthesis.

DMP has been employed in a practical and efficient route for the one-step conversion of aromatic and aliphatic aldehydes to acyl azides (Scheme 16). The acyl azides are able to be isolated without rearrangement to the alkyl isocyanate due to the mild reaction conditions.3


Scheme 16

Intramolecular competition between a dihydropyridine and isoxazolyl alcohols has also been reported. When oxidation was performed using one equivalent of DMP, the keto-isoxazole-dihydropyridine was produced in 93% isolated yield, with no detectable oxidation of the dihydropyridine (Scheme 17).4


Scheme 17

A recent report describes a useful procedure for the removal of thioacetals and thioketals using DMP, displaying compatibility with a wide range of functional groups (Scheme 18). A direct route to the corresponding acetals is also possible when the transformation is performed in the presence of an alcohol (Scheme 19).5


Scheme 18


Scheme 19

Rare, complex, and diverse polycycles and heterocycles can be rapidly obtained through DMP-mediated cascade cyclization (Scheme 20).6,7


Scheme 20

A slight modification in the reaction conditions allows for the generation of p-quinones from anilides. This approach was then used as a key step in concise and efficient syntheses of epoxyquinomycin B (Scheme 21) and topoisomerase-II inhibitor BE-10988 (Scheme 22).8


Scheme 21


Scheme 22

Dess–Martin periodinane was found to be a superior oxidant for the efficient preparation of epimerization-sensitive, optically active N-protected α-amino aldehydes with high enantiomeric excess (Scheme 23).9


Scheme 23

DMP-mediated oxidation also provides a convenient route to the preparation of highly reactive acyl nitroso compounds. These products can be trapped by dienes to form cycloadducts (Scheme 24).10


Scheme 24

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References

  1. Dess, D.B and Martin, J. C. J. Org. Chem. 1983, 48, 4155.
  2. Yadav, J. S. et al. Tetrahedron 2004, 60, 2131.
  3. Bose, D. S. and Reddy, A. V. N. Tetrahedron Lett. 2003, 44, 3543.
  4. Nelson, J. K. et al. Synlett 2003, 2213.
  5. Langille, N. F. et al. Org. Lett. 2003, 5, 575.
  6. Kitamura, T. and Mori, M. Org. Lett. 2001, 3, 1161.
  7. Nicolaou, K. C. et al. J. Am. Chem. Soc. 2002, 124, 2212.
  8. Nicolaou, K. C. et al. J. Am. Chem. Soc. 2002, 124, 2221.
  9. Myers, A. G. et al. Tetrahedron Lett. 2000, 41, 1359.
  10. Jenkins, N. E. et al. Synth. Commun. 2000, 30, 947.

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