Chromium Catalyzed Oxidation of (Homo-)Allylic and (Homo-)Propargylic Alcohols with Sodium Periodate to Ketones or Carboxylic Acids

Lizette Schmieder-van de Vondervoort; Sabine Bouttemy; José M. Padrón; Jean Le Bras; Jacques Muzart; Paul L. Alsters

doi:10.1055/s-2002-19771

LETTER

Chromium Catalyzed Oxidation of (Homo-)Allylic and (Homo-)Propargylic Alcohols with Sodium Periodate to Ketones or Carboxylic Acids

Lizette Schmieder-van de Vondervoort^a, Sabine Bouttemy^a, José M. Padrón^a, Jean Le Bras^b, Jacques Muzart^b, Paul L. Alsters*^a
^a DSM Fine Chemicals-Advanced Synthesis and Catalysis, P.O. Box 18, 6160 MD Geleen, The Netherlands
Fax: +31(46)4767604; e-Mail: paul.alsters@dsm.com;
^b Unité Mixte de Recherche Réactions Sélectives et Applications, CNRS, Université de Reims Champagne-Ardenne, B.P. 1039, 51687 Reims Cedex 2, France
Fax: +33(3)26913166; e-Mail: jacques.muzart@univ-reims.fr;

Abstract

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Abstract

Primary and secondary (homo-)allylic and (homo-)propargylic alcohols can be oxidized under slightly acidic conditions at or below room- temperature with sodium periodate in the presence of sodium dichromate as the catalyst to the corresponding carboxylic acids and ketones, respectively.

Key words

alcohols - catalysis - oxidations - sodium periodate - sodium dichromate

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References

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Typical Procedure; preparation of 5-hexyn-3-one: A 250 mL jacketed reactor, equipped with a mechanical stirrer, was charged with water (90 mL), 65% aq HNO₃ (0.49 g; 5 mmol HNO₃), and Na₂Cr₂O₇.2H₂O (0.300 g; 1 mmol). The solution was cooled to 0 °C, and NaIO₄ (23.53 g; 110 mmol) was added at maximum speed of mechanical stirring. Subsequently, a cooled solution (0 °C) of 5-hexyn-3-ol (9.86 g; 100 mmol) in CHCl₃ (90 mL) was added in one portion. The mixture was vigorously stirred for 24 h at 0 °C. The organic phase was separated from the aqueous slurry, which was subsequently extracted with CH₂Cl₂ (2 × 100 mL). After drying (Na₂SO₄) of the combined organic phases and evaporation of the solvents at 20 °C/150 mbar, a yellow oil was obtained, which according to NMR consisted of pure 5-hexyn-3-one (9.1 g; 95% yield). The product is unstable and should be stored in the freezer. ¹H NMR (CDCl₃): 3.15 (d), 2.51 (q), 2.15 (t), 0.93 (t). ¹³C NMR (CDCl₃): 204.7, 77.0, 73.1, 34.9, 33.6, 7.8. Other reactions were carried out similarly; see Table [1] for experimental details.

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During Cr(VI) catalyzed alcohol oxidation with periodic acid, a similar formation of a green Cr(III) species was observed, see ref. [9]

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