Abstract
The oxidation of alcohols to carbonyl compounds such as aldehydes and ketones was studied using potassium hexacyanoferrate(III) mediated by nitroxyl radical polystyrene resins as catalyst under organic-aqueous two-phase conditions. Primary alcohols are readily oxidized to the corresponding aldehydes in excellent yield with no overoxidation to carboxylic acids. Secondary alcohols are converted to the corresponding ketones with a much lower efficiency. Oxidative cyclization of 1,4- and 1,5-diols to γ- and δ-lactones, respectively, proceeded nicely.
Key words
nitroxyl radical resin - potassium hexacyanoferrate(III) - alcohol - oxidation - two-phase conditions
References and Notes
1 Rozantsen EG.
Sholle VD.
Synthesis
1971,
401
2 de Nooy AEJ.
Besemer AC.
van Bekkum H.
Synthesis
1996,
1153
3 Sheldon RA.
Arends ICWE.
Adv. Synth. Catal.
2004,
346:
1051
4 But TYS.
Tashino Y.
Togo H.
Toy PH.
Org. Biomol. Chem.
2005,
3:
970
5 Ley SV.
Baxendal IR.
Bream RN.
Jackson PS.
Leach AG.
Longbottom DA.
Nesi M.
Scott JS.
Storer RI.
Taylor SJ.
J. Chem. Soc., Perkin Trans. 1
2000,
3815
6 Weik S.
Nicholson G.
Jung G.
Rademann J.
Angew. Chem. Int. Ed.
2004,
40:
1436
7 Bolm C.
Magnus AS.
Hildebrand JP.
Org. Lett.
2000,
2:
1173
8 Pozzi G.
Cavazzini M.
Quici S.
Benaglia M.
Dell’Anna G.
Org. Lett.
2004,
6:
441
9 Ferreira P.
Phillips E.
Rippon D.
Tsang SC.
Hayes W.
J. Org. Chem.
2004,
69:
6851
10 Dijksman A.
Arends IWCE.
Sheldon RA.
Chem. Commun.
2000,
271
11 Wu X.-E.
Ma L.
Ding M.-X.
Gao L.-X.
Synlett
2005,
607
12a Anelli PL.
Biffi C.
Montanari F.
Quici S.
J. Org. Chem.
1987,
52:
2559
12b Anelli PL.
Biffi C.
Montanari F.
Quici S.
J. Org. Chem.
1989,
54:
2970
12c Anelli PL.
Montanari F.
Quici S.
Org. Synth.
1990,
69:
212
12d Siedlecka R.
Skarzewski J.
Mlochowski J.
Tetrahedron Lett.
1990,
31:
2177
12e Tong G.
Perich JW.
Johns RB.
Tetrahedron Lett.
1990,
31:
3759
12f Straub ST.
J. Chem. Educ.
1991,
68:
1048
12g Davis NJ.
Flitsch SL.
Tetrahedron Lett.
1993,
34:
1181
12h Davis NJ.
Flitsch SL.
J. Chem. Soc., Perkin Trans. 1
1994,
359
12i Bolm C.
Fey T.
Chem. Commun.
1999,
1795
12j Zao M.
Li J.
Mano E.
Song Z.
Tschaen DM.
Grabowski EJJ.
Reider PJ.
J. Org. Chem.
1999,
64:
2564
13a Leanna MR.
Sowin TJ.
Morton HE.
Tetrahedron Lett.
1992,
33:
5029
13b Inokuchi T.
Matsumoto S.
Nishiyama T.
Torii S.
Synlett
1990,
57
13c Inokuchi T.
Matsumoto S.
Torii S.
J. Org. Chem.
1991,
56:
2416
13d Ogibin YuN.
Khusid AKh.
Nikishin GI.
Bull. Acad. Sci., USSR, Div. Chem. Sci.
1992,
735
13e Kuroboshi M.
Yoshihara H.
Cortona MN.
Kawakami Y.
Gao Z.
Tanaka H.
Tetrahedron Lett.
2000,
41:
8131
2 :
14a Inokuchi T.
Matsumoto S.
Nishiyama T.
Torii S.
J. Org. Chem.
1990,
55:
462
14b Inokuchi T.
Liu P.
Torii S.
Chem. Lett.
1994,
1411
14c Saito S.
Hara T.
Naka K.
Hayashi T.
Moriwake T.
Synlett
1992,
241
14d Saito S.
Ishikawa T.
Moriwake T.
Synlett
1993,
139
15 4 NBr3 : Inokuchi T.
Matsumoto S.
Fukushima M.
Torii S.
Bull. Chem. Soc. Jpn.
1991,
64:
796
2 :
16a Miyazawa T.
Endo T.
J. Mol. Catal.
1985,
31:
217
16b Miyazawa T.
Endo T.
J. Polym. Sci., Part A: Polym. Chem.
1985,
23:
2487
3 Fe(CN)6 :
17a Miyazawa T.
Endo T.
J. Mol. Catal.
1985,
32:
357
17b Miyazawa T.
Endo T.
J. Mol. Catal.
1988,
49:
L31
17c Kashiwagi Y.
Chiba S.
Anzai J.
New J. Chem.
2003,
27:
1545
18 During the oxidation reaction, some of the polymer beads were removed from the reaction solution and extracted. The product was identified by comparing its retention time on HLPC or/and GC with those of an authentic sample. HPLC analysis was carried out using Daicel CHIRALCEL® OD column (46 mm × 250 mm). The column temperature was kept constant at 40 °C. The analytes were eluted by i- PrOH-n -hexane (2:33) at 0.7 mL min-1 flow rate, and detected by UV adsorption at 254 nm. The GC analysis was carried out using CP-Cyclodextrin-B-2,3,6-M-19 capillary column (0.25 mm × 25 m). The column temperature increased at 3 °C min-1 from 80 °C to 150 °C. The injection and detector temperatures were kept constant at 200 °C and 240 °C, respectively.
19a Kishioka S.
Ohsaka T.
Tokuda K.
Chem. Lett.
1998,
343
19b Kishioka S.
Ohki S.
Ohsaka T.
Tokuda K.
J. Electroanal. Chem.
1998,
452:
176
