Download PDF
Synlett 2006(18): 3057-3060  
DOI: 10.1055/s-2006-951501
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Sterically Bulky Cyclic Thiourea as an Efficient Ligand for Palladium-Catalyzed Aerobic Oxidation of Alcohols

Min Yanga, Kai-Tai Yipa, Jie-Hui Pana, Ying-Chun Chenb, Nian-Yong Zhua, Dan Yang*a
a Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. of China
Fax: +85228592159; e-Mail: yangdan@hku.hk;
b Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. of China
Further Information

Publication History

Received 17 April 2006
Publication Date:
25 October 2006 (online)

    Permissions and Reprints All articles of this category

Abstract

Sterically bulky N,N¢-disubstituted cyclic thiourea ligand L1 has been demonstrated as an efficient ligand in palladium-catalyzed oxidation of alcohols using molecular oxygen as an oxidant. This new catalyst system has been applied to a wide variety of substrates such as benzylic alcohols, aliphatic secondary alcohols and allylic alcohols, producing the corresponding carbonyl compounds in good to excellent yields.

Key words

ligands - palladium - homogenous catalysis - alcohols - oxidation

    References and Notes

  • 1a Parshall GD. Ittel SD. Homogeneous Catalysis   John Wiley and Sons; New York: 1992.  p.168 
    Google Scholar
  • 1b Mark UIE. Giles PR. Tsukazaki M. Brown SM. Urch CJ. In Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals   Vol. 2:  Beller M. Bolm C. Wiley-VCH; New York: 1998.  p.350-360  
    Google Scholar
  • 2a van Leeuwen PWNM. Appl. Catal., A  2001,  212:  61 
    CrossrefPubMedGoogle Scholar
  • 2b Sheldon RA. Arends IWCE. ten Brink G.-J. Dijksman A. Acc. Chem. Res.  2002,  35:  774 
    CrossrefPubMedGoogle Scholar
  • 2c Stahl SS. Angew. Chem. Int. Ed.  2004,  43:  3400 
    CrossrefPubMedGoogle Scholar
  • 3 Peterson KP. Larock RC. J. Org. Chem.  1998,  63:  3185 
    CrossrefGoogle Scholar
  • 4a Nishimura T. Onoue T. Ohe K. Uemura S. Tetrahedron Lett.  1998,  39:  6011 
    Google Scholar
  • 4b Nishimura T. Onoue T. Ohe L. Uemura S. J. Org. Chem.  1999,  64:  6750 
    Google Scholar
  • 4c Nishimura T. Maeda Y. Kakiuchi N. Uemura S. J. Chem. Soc., Perkin Trans. 1  2000,  4301 
    Google Scholar
  • 4d Iwasawa T. Tokunaga M. Obora Y. Tsuji Y. J. Am. Chem. Soc.  2004,  126:  6554 
    Google Scholar
  • 4e Schultz MJ. Hamilton SS. Jensen DR. Sigman MS. J. Org. Chem.  2005,  70:  3343 
    Google Scholar
  • 5 Schultz MJ. Park CC. Sigman MS. Chem. Commun.  2002,  3034 
    CrossrefGoogle Scholar
  • 6a Hallman K. Moberg C. Adv. Synth. Catal.  2001,  343:  260 
    CrossrefGoogle Scholar
  • 6b Paavola S. Zetterberg K. Privalov T. Csöregh I. Moberg C. Adv. Synth. Catal.  2004,  346:  237 
    CrossrefGoogle Scholar
  • 7a Jensen DR. Schultz MJ. Mueller JA. Sigman MS. Angew. Chem. Int. Ed.  2003,  42:  3810 
    Google Scholar
  • 7b

    Ref. 4e.

  • 8a Brink G.-J. Arends IWCE. Sheldon RA. Science  2000,  287:  1636 
    CrossrefGoogle Scholar
  • 8b Brink G.-J. Arends IWCE. Hoogenraad M. Verspui G. Sheldon RA. Adv. Synth. Catal.  2003,  345:  1341 
    CrossrefGoogle Scholar
  • 9a Munno GD. Gabriele B. Salerno G. Inorg. Chim. Acta  1995,  234:  181 
    Google Scholar
  • 9b Gabriele B. Salerno G. Costa M. Chiusoli GP. J. Organomet. Chem.  1995,  503:  21 
    Google Scholar
  • 9c Touchard F. Fache F. Lemaire M. Tetrahedron: Asymmetry  1997,  8:  3319 
    Google Scholar
  • 9d Touchard F. Gamez P. Fache F. Lemaire M. Tetrahedron Lett.  1997,  38:  2275 
    Google Scholar
  • 9e Touchard F. Bernard M. Fache F. Delbecq F. Guiral V. Sautet P. Lemaire M. J. Organomet. Chem.  1998,  567:  133 
    Google Scholar
  • 9f Touchard F. Bernard M. Fache F. Lemaire M. J. Mol. Catal. A: Chem.  1999,  140:  1 
    Google Scholar
  • 9g Zhang TY. Allen MJ. Tetrahedron Lett.  1999,  40:  5813 
    Google Scholar
  • 9h Tommasino ML. Casalta M. Breuzard JAJ. Lemaire M. Tetrahedron: Asymmetry  2000,  11:  4835 
    Google Scholar
  • 9i Breuzard JAJ. Tommasino ML. Touchard F. Lemaire M. Bonnet MC. J. Mol. Catal. A: Chem.  2000,  156:  223 
    Google Scholar
  • 9j Nan Y. Miao H. Yang Z. Org. Lett.  2000,  2:  297 
    Google Scholar
  • 9k Miao H. Yang Z. Org. Lett.  2000,  2:  1765 
    Google Scholar
  • 9l Hu Y. Yang Z. Org. Lett.  2001,  3:  1387 
    Google Scholar
  • 9m Kovala-Demertzi D. Yadav PN. Demertzis MA. Jasiski JP. Andreadaki FJ. Kostas ID. Tetrahedron Lett.  2004,  45:  2923 
    Google Scholar
  • 9n Tang Y. Deng LY. Zhang G. Dong J. Yang Z. Org. Lett.  2005,  7:  593 ; and references cited therein
    Google Scholar
  • 10a Dai M. Wang C. Liang B. Chen J. Yang Z. Eur. J. Org. Chem.  2003,  4346 
    CrossrefGoogle Scholar
  • 10b Dai M. Liang B. Wang C. Chen J. Yang Z. Org. Lett.  2004,  6:  221 
    CrossrefGoogle Scholar
  • 10c Dai M. Liang B. Wang C. You JZ. Yang Z. Adv. Synth. Catal.  2004,  346:  1669 
    CrossrefGoogle Scholar
  • 11a Yang D. Chen Y.-C. Zhu N.-Y. Org. Lett.  2004,  6:  1577 
    CrossrefGoogle Scholar
  • 11b Chen W. Li R. Han B. Li B.-J. Chen Y.-C. Wu Y. Ding L.-S. Yang D. Eur. J. Org. Chem.  2006,  1177 
    CrossrefGoogle Scholar
  • 12 Komano T. Iwasawa T. Tokunaga M. Obora Y. Tsuji Y. Org. Lett.  2005,  7:  4677 
    CrossrefGoogle Scholar
  • 15 Whitesell JK. Chem. Rev.  1989,  89:  1581 
    CrossrefGoogle Scholar
13

L1 is a highly efficient ligand for Heck reactions; see ref. 11a. L2-4 were prepared following the similar procedures.

14

Other reaction parameters, including palladium sources, solvents, and bases, were examined and the reported conditions were found optimal. The effect of 3 Å molecular sieves was found to give deleterious effect on yields because of serious Pd-black formation.