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

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

References

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• 9 A related Cr catalyzed method based on periodic acid has recently been reported: Zhao M. Li J. Song Z. Desmond R. Tschaen DM. Grabowski EJJ. Reider PJ. Tetrahedron Lett.  1998,  39:  5323 ; this method obviously works under much more acidic conditions than the present sodium periodate method, which uses a catalytic amount of acid
• 11a

  Ref. [1] , p 315, 349.

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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]