Download PDF
Synlett 2010(3): 437-440  
DOI: 10.1055/s-0029-1219202
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

In situ Formation of NOx and Br Anion for Aerobic Oxidation of Benzylic Alcohols without Transition Metal

Guanyu Yang*a, Wei Wanga, Weimin Zhua, Cunbin Ana, Xinqin Gaob, Maoping Song*a
a Department of Chemistry, Zhengzhou University, 75 Daxue Road, Zhengzhou 450052, P. R. of China
Fax: +86(371)67763927; e-Mail: yangguanyu@zzu.edu.cn; e-Mail: mpsong9350@zzu.edu.cn;
b State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, P. R. of China
Further Information

Publication History

Received 20 October 2009
Publication Date:
15 January 2010 (online)

   Permissions and Reprints All articles of this category
Preview

Abstract

The reaction of KBrO3 and NH2OH˙HCl in situ generates NOx and Br anion, which combine with 2,2,6,6-tetramethylpiperidine-N-oxide (TEMPO) to construct a NO-activating dioxygen, Br-assisted, TEMPO-catalyzed aerobic oxidation of alcohols. Catalyzed by KBrO/NH2OH˙HCl/TEMPO, various benzylic alcohols can be oxidized quantitatively to their corresponding carbonyl compounds under mild conditions. The easy handling and simple product separation make the process an attractive candidate for the oxidation of alcohols.

Key words

oxidation - alcohols - catalyst - bromate - hydroxylammonium - 2,2,6,6-tetramethylpiperidine-N-oxide

    References and Notes

  • 1a Caron S. Dugger RWS. Ruggeri G. Ragan JA. Ripin DHB. Chem. Rev.  2006,  106:  2943 
    Search in Google Scholar
  • 1b Zhan B. Thompson A. Tetrahedron  2004,  60:  2917 
    Search in Google Scholar
  • 1c Tashiro A. Mitsuishi A. Irie R. Katsuki T. Synlett  2003,  1868 
  • 1d Qian W. Jin E. Bao W. Zhang Y. Angew. Chem. Int. Ed.  2005,  44:  952 
    Search in Google Scholar
  • 1e Minisci F. Porta O. Recupero F. Punta C. Gambarotti C. Pierini M. Galimberti L. Synlett  2004,  2203 
  • 1f Lenoir D. Angew. Chem. Int. Ed.  2006,  45:  3206 
    Search in Google Scholar
  • 1g Friedrich HB. Khan F. Singh N. van Staden M. Synlett  2001,  869 
  • 1h Miyamura H. Matsubara R. Miyazaki Y. Kobayashi S. Angew. Chem.Int. Ed.  2007,  46:  4151 
    Search in Google Scholar
  • 1i Sharma VB. Jain SL. Sain B. Synlett  2005,  173 
  • 1j Lei Z. Yang Y. Bai X. Adv. Synth. Catal.  2006,  348:  877 
    Search in Google Scholar
  • 2a Sheldon RA. Arends IWCE. J. Mol. Catal. A: Chem.  2006,  251:  2 
    Search in Google Scholar
  • 2b Minisci F. Punta C. Recupero F. J. Mol. Catal. A: Chem.  2006,  251:  129 
    Search in Google Scholar
  • 2c Nabyl M. Synlett  2003,  1757 
  • 2d Bailey WF. Bobbitt JM. J. Org. Chem.  2007,  72:  4504 
    Search in Google Scholar
  • 2e Karimi B. Biglari A. Clark JH. Budarin V. Angew. Chem. Int. Ed.  2007,  46:  7210 
    Search in Google Scholar
  • 2f Susana B. Synlett  2001,  563 
  • 2g Félix C. Synlett  2006,  657 
  • 2h Vatèle J.-M. Synlett  2006,  2055 
  • 2i Holczknecht O. Cavazzini M. Quici S. Shepperson I. Pozzi G. Adv. Synth. Catal.  2005,  347:  677 
    Search in Google Scholar
  • 2j Yang G. Guo Y. Wu G. Zheng L. Song M. Prog. Chem.  2007,  19:  1727 
    Search in Google Scholar
  • 2k Luca LD. Giacomelli G. Porcheddu A. Org. Lett.  2001,  3:  3041 
    Search in Google Scholar
  • 2l Jiang N. Ragauskas AJ. J. Org. Chem.  2006,  71:  7087 
    Search in Google Scholar
  • 2m Herrerías CI. Zhang TY. Li C.-J. Tetrahedron Lett.  2006,  47:  13 
    Search in Google Scholar
  • 3a Yang G. Zhu W. Zhang P. Xue H. Wang W. Tian J. Song M. Adv. Synth. Catal.  2008,  350:  542 
    Search in Google Scholar
  • 3b Yang G. Ma J. Wang W. Zhao J. Lin X. Zhou L. Gao X. Catal. Lett.  2006,  112:  83 
    Search in Google Scholar
  • 3c Guo Y. Zhao J. Xu J. Wang W. Tian F. Yang G. Song M. J. Nat. Gas Chem.  2007,  16:  210 
    Search in Google Scholar
  • 4 Wang N. Liu R. Chen J. Liang X. Chem. Commun.  2005,  5322 
    Crossref
  • 5 Cecchetto A. Fontana F. Miniscia F. Recupero F. Tetrahedron Lett.  2001,  42:  6651 
    CrossrefSearch in Google Scholar
  • 6a Gamez P. Arends IWCE. Reedijk J. Sheldon RA. Chem. Commun.  2003,  2414 
  • 6b Figiel PJ. Leskelä M. Repo T. Adv. Synth. Catal.  2007,  349:  1173 
    Search in Google Scholar
  • 7a Dijksman A. Arends IWCE. Sheldon RA. Chem. Commun.  1999,  1591 
  • 7b Dijksman A. Marino-González A. Payeras AM. Arends IWCE. Sheldon RA.
    J. Am. Chem. Soc.  2001,  123:  6826 
    Search in Google Scholar
  • 8 Liu R. Liang X. Dong C. Hu X. J. Am. Chem. Soc.  2004,  126:  4112 
    CrossrefPubMedSearch in Google Scholar
  • 9 Liu R. Dong C. Liang X. Wang X. Hu X. J. Org. Chem.  2005,  70:  729 
    CrossrefPubMedSearch in Google Scholar
  • 10 Xie Y. Mo W. Xu D. Shen Z. Sun N. Hu B. Hu X. J. Org. Chem.  2007,  72:  4288 
    CrossrefPubMedSearch in Google Scholar
  • 11 Jonnalagadda SB. Shezi MN. J. Phys. Chem. A  2009,  113:  5540 
    CrossrefPubMedSearch in Google Scholar
12

General Typical Procedure for the Oxidation
The reaction was carried out in a 70 mL autoclave, and the general procedure is described typically with benzyl alcohol as follows: To a reactor were added benzyl alcohol (2 mL, 19.3 mmol), NH2OH˙HCl (174.8 mg, 10 mol%), KBrO3 (161.2 mg, 5 mol%), TEMPO (15.1 mg, 0.5 mol%), and CH2Cl2 (10 mL). The closed autoclave was charged with O2 to 0.3 MPa and warmed to 80 ˚C under stirring. The pressure of O2 was kept under 0.4 MPa for 2 h. After cooled to r.t., 20 mL CH2Cl2 were added to the autoclave. Then the solution was analyzed by gas chromatography, which was conducted using an Agilent Technologies 6890N Network GC System with a flame ionization detector and a DB-1 capillary column (30 m × 0.535 mm × 3.0 µm).

13

General Isolation Procedure for the Oxidation Product
After GC showed the reaction to be complete, the reaction mixture was diluted with CH2Cl2 and transferred into a separation funnel. The CH2Cl2 solution was washed with 15 mL of a sat. solution of Na2CO3, followed by brine. The organic layer was dried over anhyd Na2SO4, and the solvent was evaporated to yield the product without further purification.