Synlett 2012; 23(11): 1683-1685
DOI: 10.1055/s-0031-1290367
letter
© Georg Thieme Verlag Stuttgart · New York

Oxidation of Secondary Benzylic Alcohols to Ketones and Benzylic Oxy­genation of Alkylarenes with Hydrogen Peroxide in the Presence of Activated Carbon

Shunsuke Nishida
Department of Chemistry, Graduate School of Science, Kobe University, Nada, Kobe 657-8501, Japan, Fax: +81(78)8035688   eMail: mhayashi@kobe-u.ac.jp
,
Masahiko Hayashi*
Department of Chemistry, Graduate School of Science, Kobe University, Nada, Kobe 657-8501, Japan, Fax: +81(78)8035688   eMail: mhayashi@kobe-u.ac.jp
› Institutsangaben
Weitere Informationen

Publikationsverlauf

Received: 23. März 2012

Accepted after revision: 19. April 2012

Publikationsdatum:
13. Juni 2012 (online)


Abstract

A variety of benzylic alcohols were oxidized to the corresponding carbonyl compounds selectively with 30% hydrogen peroxide (H2O2) in the presence of activated carbon. Alkylarenes such as fluorenes, xanthenes, and anthrone were also effectively oxygenated to the corresponding carbonyl compounds with 30% H2O2 as oxidant in the presence of activated carbon.

Supporting Information

 
  • References and Notes

    • 1a Sheldon A, Kochi JK. Metal-Catalyzed Oxidations of Organic Compounds . Academic Press; New York: 1984
    • 1b Hudlicky M. Oxidations in Organic Chemistry . ACS Monograph Series, ACS; Washington, DC: 1990
    • 1c Tojo G, Fernandez M. Oxidation of Alcohols to Aldehydes and Ketones 2006
    • 1d Hayashi M, Kawabata H. Environmentally Benign Oxidation of Alcohols Using Transition-Metal Catalysts. In Advances in Chemistry Research. Gerard FL. Nova Science Publishers; New York: 2006: 45
  • 2 Bowden K, Heilbron IM, Jones ER. H, Weedon BC. L. J. Chem. Soc. 1946; 39
    • 3a Corey EJ, Suggs JW. Tetrahedron Lett. 1975; 2647
    • 3b Brown HC, Rao CG, Kulkarni SU. J. Org. Chem. 1979; 44: 2809
  • 4 Corey EJ, Schmidt G. Tetrahedron Lett. 1979; 399
  • 5 Mancuso AJ, Swern D. Synthesis 1981; 165
  • 6 Dess DB, Martin JC. J. Am. Chem. Soc. 1991; 113: 7277
  • 7 Cella JA, Kelley JA, Kenehan EF. J. Org. Chem. 1975; 40: 860
  • 8 Markó IE, Giles PR, Tsukazaki M, Brown SM, Urch CJ. Science 1996; 274: 2044
  • 9 Markó IE, Giles PR, Tsukazaki M, Chelle-Regnaut I, Urch CJ, Brown SM. J. Am. Chem. Soc. 1997; 119: 12661
  • 10 Sato K, Aoki M, Takagi J, Noyori R. J. Am. Chem. Soc. 1997; 119: 12386
  • 11 Hayashi M, Yamada K, Nakayama S, Hayashi H, Yamazaki S. Green Chem. 2000; 257
  • 12 Sano Y, Tanaka T, Hayashi M. Chem. Lett. 2007; 36: 1414
    • 13a Fukuda O, Sakaguchi S, Ishii Y. Adv. Synth. Catal. 2001; 343: 809
    • 13b Tashiro Y, Iwahama T, Sakaguchi S, Ishii Y. Adv. Synth. Catal. 2001; 343: 220
    • 13c Shibamoto A, Sakaguchi S, Ishii Y. Org. Process Res. Dev. 2000; 4: 505
    • 13d Matsunaka K, Iwahama T, Sakaguchi S, Ishii Y. Tetrahedron Lett. 1999; 40: 2165
    • 13e Ishii Y, Nakayama K, Takeno M, Sakaguchi S, Iwahama T, Nishiyama Y. J. Org. Chem. 1995; 60: 3934
  • 14 Yamaguchi K, Mizuno N. New J. Chem. 2002; 26: 972
  • 15 Matsushita T, Ebitani K, Kaneda K. Chem. Commun. 1999; 265
  • 16 Barbiero G, Kim W.-G, Hay AS. Tetrahedron Lett. 1994; 35: 5833
    • 17a Maikap GC, Guhathakurta D, Iqbal J. Synlett 1995; 189
    • 17b Punniyamurthy T, Iqbal J. Tetrahedron Lett. 1994; 35: 4003
  • 18 Santamaria J, Jroundi R. Tetrahedron Lett. 1991; 32: 4291
  • 19 Singh KN, Singh S. Bull. Electrochem. 2000; 16: 385
    • 20a Hayashi M. Chem. Rec. 2008; 8: 252
    • 20b Kawashita Y, Yanagi J, Fujii T, Hayashi M. Bull. Chem. Soc. Jpn. 2009; 82: 482
  • 21 The detail of urea–H2O2-activated carbon system will be published in a separate paper
  • 22 General Experimental Procedure A mixture of alcohol (1 mmol), 100 wt% of activated carbon [Charcoal Activated, Tokyo Chemical Industry Co., Ltd (TCI)], 30% H2O2 (10 mmol), and anhyd xylene (10 mL) was placed in a three-necked flask. The whole was heated to 95 °C and stirred for 18 h at this temperature. After confirmation of the completion of the reaction by TLC analysis (hexane–EtOAc = 1:2), activated carbon was filtered off using Celite. The filtrate was evaporated and then silica gel column chromatographed or recrystallized to afford the carbonyl compound