Abstract
A selective oxidation of secondary alcohols to the corresponding ketones in room temperature
ionic liquid was achieved by using copper acetylacetonate/tert -butylhydroperoxide system. The catalytic system can be recycled and reused for five
runs without any significant loss of catalytic activity and products are obtained
in excellent yield.
Key words
copper acetylacetonate - oxidation -
sec -alcohols - ionic liquid - catalyst
References and Notes
<A NAME="RW24306ST-1">1 </A>
Ley SV.
Madin A. In Comprehensive Organic Synthesis
Vol. 7:
Trost BM.
Fleming I.
Pergamon;
Oxford:
1991.
p.305
<A NAME="RW24306ST-2">2 </A>
Ley SV.
Madin A. In Comprehensive Organic Synthesis
Vol. 7:
Trost BM.
Fleming I.
Pergamon;
Oxford:
1991.
p.251
3a </A>
Marko IE.
Giles PR.
Tsukazaki M.
Brown SM.
Urch CJ.
Science
1996,
274:
2044
3b </A>
Saint-Aman E.
Menage S.
Pierre J.-L.
Defrancq E.
Gellon G.
New J. Chem.
1998,
393
3c </A>
Chaudhuri P.
Hess M.
Mueller J.
Hildenbrand K.
Bill E.
Weyhermueller T.
Wieghardt K.
J. Am. Chem. Soc.
1999,
121:
9599
3d </A>
Marko IE.
Gautier A.
Dumeunier R.
Doda K.
Philippart F.
Brown SM.
Urch CJ.
Angew. Chem. Int. Ed.
2004,
43:
1588
3e </A>
Gamez P.
Arends IWCE.
Reedijk J.
Sheldon RA.
Chem. Commun.
2003,
2414
3f </A>
Velusamy S.
Srinivasan A.
Punniyamurthy T.
Tetrahedron Lett.
2006,
47:
923
<A NAME="RW24306ST-4">4 </A>
Sirkecioglu O.
Karliga B.
Talinli N.
Tetrahedron Lett.
2003,
44:
8483
<A NAME="RW24306ST-5">5 </A>
Hanaya K.
Muramatsu T.
Kudo H.
J. Chem. Soc., Perkin Trans. 1
1979,
2409
<A NAME="RW24306ST-6">6 </A>
Kantam ML.
Kavita VNB.
Haritha Y.
Synlett
2004,
525
<A NAME="RW24306ST-7">7 </A>
Aggarwal VK.
Synlett
1998,
329
<A NAME="RW24306ST-8">8 </A>
Alizadeh M.
Farzaneh F.
Ghandi M.
J. Mol. Catal. A: Chem.
2003,
194:
283
9a </A>
Kantam ML.
Neeraja V.
Kavita B.
Neelima B.
Chaudhuri MK.
Hussain S.
Adv. Synth. Catal.
2005,
347:
763
9b </A>
Kantam ML.
Neelima B.
Reddy CV.
J. Mol. Catal. A: Chem.
2006,
256:
269
9c </A>
Kantam ML.
Kavita B.
Neeraja V.
Haritha Y.
Chaudhuri MK.
Dehury SK.
Adv. Synth. Catal.
2005,
347:
641
<A NAME="RW24306ST-10">10 </A>
Muzart J.
Adv. Synth. Catal.
2006,
348:
275
11a </A>
Seddon KR.
Stark A.
Green Chem.
2002,
4:
119
11b </A>
Ganchegui B.
Bouquillon S.
Hénin F.
Muzart J.
Tetrahedron Lett.
2002,
43:
6641
11c </A>
Muzart J.
Tetrahedron
2003,
59:
5789
11d </A>
Bouquillon S.
du Moulinet d’Hardemare A.
Averbuch-Pouchot M.-Th.
Hénin F.
Muzart J.
Polyhedron
1998-1999,
18:
3511
11e </A>
Ganchegui B.
Bouquillon S.
Hénin F.
Muzart J.
J. Mol. Catal. A: Chem.
2004,
214:
65
11f </A>
Hardacre C.
Mullan EA.
Rooney DW.
Thompson JM.
J. Catal.
2005,
232:
355
12a </A>
Wolfson A.
Wuyts S.
De Vos DE.
Vankelecom IFJ.
Jacobs PA.
Tetrahedron Lett.
2002,
43:
8107
12b </A>
Tang WM.
Li CJ.
Acta Chim. Sin.
2004,
62:
742
<A NAME="RW24306ST-13">13 </A>
Li JW.
Sun W.
Xu LW.
Xia CG.
Wang HW.
Chin. Chem. Lett.
2004,
15:
1437
14a </A>
Chhikara BS.
Tehlan S.
Kumar A.
Synlett
2005,
63
14b </A>
Chhikara BS.
Chandra R.
Tandon V.
J. Catal.
2005,
230:
436
<A NAME="RW24306ST-15">15 </A>
Bianchini G.
Crucianelli M.
De Angelis F.
Neri V.
Saladino R.
Tetrahedron Lett.
2005,
46:
2427
16a </A>
Ansari IA.
Gree R.
Org. Lett.
2002,
4:
1507
16b </A>
Jiang N.
Ragauskas AJ.
Org. Lett.
2005,
7:
3689
16c </A>
Wu XE.
Ma L.
Ding MX.
Gao LX.
Chem. Lett.
2005,
34:
312
17 </A>
Representative Procedure for the Oxidation of Secondary Alcohols.
A mixture of cyclohexanol (2 mmol), copper acetylacetonate [Cu(acac)2 , 0.06 mmol] and t -BuOOH (10 mmol) was added in a microreactor under magnetic stirring for 1 min, and
[bmim]PF6 (1 mL) was added to the mixture. After 10 min of stirring, the blue color of the
reaction mixture turned into dark green color. The reaction mixture was stirred at
r.t. for 5 h and then extracted with n -hexane (3 × 5 mL). The combined n -hexane phase was concentrated in vacuo and monitored by GC and 1 H NMR. Then the residue was purified by flash chromatography to afford cyclohexanone
(51% yield).
