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
1 Tidwell TT. In
Organic Reactions
Vol. 39:
Wiley;
New York:
1990.
p.297
2a Cainelli G.
Cardillo G.
Chromium Oxidations in Organic Chemistry
Verlag;
Berlin:
1984.
2b Luzzio FA. In
Organic Reactions
Vol. 53:
Wiley;
New York:
1998.
p.1
3a Dijksman A.
Marino-González A.
Mairata I.
Payeras A.
Arends IWCE.
Sheldon RA.
J. Am. Chem. Soc.
2001,
123:
6826 ; and references therein
3b Ben-Daniel R.
Alsters PL.
Neumann R.
J. Org. Chem.
2001,
66:
8650
3c de Nooy AEJ.
Besemer AC.
van Bekkum H.
Synthesis
1999,
1153
3d Bobbitt JM.
Flores MCL.
Heterocycles
1988,
27:
509
4a Nait Ajjou A.
Tetrahedron Lett.
2001,
42:
13 ; and references therein
4b Graauw CF.
Peters JA.
van Bekkum H.
Huskens J.
Synthesis
1994,
1007
5 Muzart J.
Chem. Rev.
1992,
92:
113
6a Soler MA.
Martín VS.
Tetrahedron Lett.
1999,
40:
2815
6b Li LT.
Ma SM.
Youji Huaxue
2000,
20:
850 ; Chem. Abstr. 2001 , 134 , 192946
7a Brandsma L.
Verkruijsse HD.
Studies in Organic Chemistry 8, Synthesis of Acetylenes, Allenes and Cumulenes
Elsevier;
Amsterdam:
1981.
p.236
7b Huché M.
Tetrahedron
1980,
36:
331
7c Crombie L.
Jacklin AG.
J. Chem. Soc.
1955,
1740
8a Le Gras J.
C. R. Acad. Sc. Paris (C)
1966,
263:
1460
8b Bertrand M.
C. R. Acad. Sc. Paris (C)
1957,
244:
1790
8c Jones ERH.
Mansfield GH.
Whiting MC.
J. Chem. Soc.
1954,
3208
9 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
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
11a Ref.
[1
11b Mancuso AJ.
Swern D.
Synthesis
1981,
165
12 Mancuso AJ.
Huang SL.
Swern D.
J. Org. Chem.
1978,
43:
2480
13 3 complex with 3,5-dimethylpyrazole is capable of oxidizing 1-octyn-3-ol: Corey EJ.
Fleet GWJ.
Tetrahedron Lett.
1973,
14:
4499
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 Na2 Cr2 O7 .2H2 O (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 CH2 Cl2 (2 × 100 mL). After drying (Na2 SO4 ) 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. 1 H NMR (CDCl3 ): 3.15 (d), 2.51 (q), 2.15 (t), 0.93 (t). 13 C NMR (CDCl3 ): 204.7, 77.0, 73.1, 34.9, 33.6, 7.8. Other reactions were carried out similarly; see Table
[1
15 Riahi A.
Hénin F.
Muzart J.
Tetrahedron Lett.
1999,
40:
2303
16 4
- rather than on total Cr(VI). At low acidity, alcohol oxidation by chromic acid proceeds very slowly because the concentration of HCrO4
- is negligible: Wiberg KB.
In Oxidation in Organic Chemistry Part A
Academic Press;
New York:
1965.
p.161
17 During Cr(VI) catalyzed alcohol oxidation with periodic acid, a similar formation of a green Cr(III) species was observed, see ref.
[9
18 Okumura A.
Kitani M.
Murata M.
Bull. Chem. Soc. Jpn.
1994,
67:
1522
