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Synlett 2002(2): 0243-0246
DOI: 10.1055/s-2002-19771
LETTER
© Georg Thieme Verlag Stuttgart · New York

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

Lizette Schmieder-van de Vondervoorta, Sabine Bouttemya, José M. Padróna, Jean Le Brasb, Jacques Muzartb, 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;
Further Information

Publication History

Received 14 November 2001
Publication Date:
02 February 2007 (online)

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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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10

An overview of homo-allylic alcohols that have been successfully oxidized without isomerization by stoichiometric Cr(VI) reagents containing organic nitrogen bases can be found in ref. [2b]

14

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.

17

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