PDF herunterladen
Synlett 2011(16): 2407-2409  
DOI: 10.1055/s-0030-1261224
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Copper-Catalyzed Domino Oxidation-Acyloxylation Reaction of 2-Arylpyridines with Aldehydes or Methylarenes

Yong-Jun Biana, Chang-Bing Xianga, Zhi-Ming Chena, Zhi-Zhen Huang*a-c
a School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. of China
Fax: +86(25)83686231.; e-Mail: huangzz@nju.edu.cn;
b Department of Chemistry, Zhejiang University, Hangzhou 310028, P. R. of China
c State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300071, P. R. of China
Weitere Informationen

Publikationsverlauf

Received 4 June 2011
Publikationsdatum:
08. September 2011 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

A domino oxidation-acyloxylation reaction of 2-aryl­pyridines with aldehydes or methylarenes under the catalysis of Cu(OAc)2 has been developed. The strategy via C-H bond functionalization has the advantages of good functional-group tolerance, high ortho regioselectivity and no need of any ligand or additive.

Key words

C-H activation - copper catalysis - domino reaction - acyloxylation - oxidation

    References and Notes

  • Papers on C-O bond formations via C-H bond functionalizations:
  • 1a Jiang H.-F. Chen H.-J. Wang A.-Z. Liu X.-H. Chem. Commun.  2010,  46:  7259 
    Google Scholar
  • 1b Zhu M.-K. Zhao J.-F. Loh T.-P. J. Am. Chem. Soc.  2010,  132:  6284 
    Google Scholar
  • 1c Van Humbeck JF. Simonovich SP. Knowles RR. MacMillan DWC. J. Am. Chem. Soc.  2010,  132:  10012 
    Google Scholar
  • 1d Terent’ev AO. Borisov DA. Yaremenko IA. Chernyshev VV. Nikishin GI. J. Org. Chem.  2010,  75:  5065 
    Google Scholar
  • 1e Mills DP. Soutar L. Lewis W. Blake AJ. Liddle ST. J. Am. Chem. Soc.  2010,  132:  14379 
    Google Scholar
  • 1f Wang G.-W. Yuan T.-T. J. Org. Chem.  2010,  75:  476 
    Google Scholar
  • 1g Ueda S. Nagasawa H. J. Org. Chem.  2009,  74:  4272 
    Google Scholar
  • 1h Wang G.-W. Yuan T.-T. Wu X.-L. J. Org. Chem.  2008,  73:  4717 
    Google Scholar
  • 1i Lee JM. Park EJ. Cho SH. Chang S. J. Am. Chem. Soc.  2008,  130:  7824 
    Google Scholar
  • 2a Dick AR. Hull KL. Sanford MS. J. Am. Chem. Soc.  2004,  126:  2300 
    Google Scholar
  • 2b Kalyani D. Sanford MS. Org. Lett.  2005,  4:  4149 
    Google Scholar
  • 2c Racowski JM. Dick AR. Sanford MS. J. Am. Chem. Soc.  2009,  131:  10974 
    Google Scholar
  • 3a Ye Z.-S. Wang W.-H. Luo F. Zhang S.-H. Cheng J. Org. Lett.  2009,  11:  3974 
    Google Scholar
  • 3b Wang W.-H. Luo F. Zhang S.-H. Cheng J. J. Org. Chem.  2010,  75:  2415 
    Google Scholar
  • 3c Wang W.-H. Pan C.-D. Chen F. Cheng J. Chem. Commun.  2011,  47:  3978 
    Google Scholar
  • 4 Chen X. Hao X.-S. Goodhua CE. Yu J.-Q. J. Am. Chem. Soc.  2006,  128:  6790 
    CrossrefPubMedGoogle Scholar
  • A book and reviews on domino or cascade reactions:
  • 5a Tietze LF. Brasche G. Gericke K. Domino Reactions in Organic Synthesis   Wiley-VCH; Weinheim: 2006. 
    Google Scholar
  • 5b Tietze LF. Chem. Rev.  1996,  96:  115 
    Google Scholar
  • 5c Wasilke JC. Obrey SJ. Baker RT. Bazan GC. Chem. Rev.  2005,  105:  1001 
    Google Scholar
  • 5d Nicolaou KC. Edmonds DJ. Bulger PG. Angew. Chem. Int. Ed.  2006,  45:  7134 
    Google Scholar
  • 5e Enders D. Grondal C. Hüttl MRM. Angew. Chem. Int. Ed.  2007,  46:  1570 
    Google Scholar
  • 5f Grondal C. Jeanty M. Enders D. Nature Chem.  2010,  2:  167 
    Google Scholar
  • 5g Westermann B. Ayaz M. Berkel SS. Angew. Chem. Int. Ed.  2010,  49:  846 
    Google Scholar
  • 6 Xiao F.-H. Shuai Q. Zhao F. Baslé O. Deng G.-J. Li C.-J. Org. Lett.  2011,  13:  1614 
    CrossrefPubMedGoogle Scholar
  • 7a Mannam S. Sekar G. Tetrahedron Lett.  2008,  49:  1083 
    Google Scholar
  • 7b Shaikh TMA. Sudalai A. Eur. J. Org. Chem.  2008,  4877 
    Google Scholar
  • 7c Rogovin M. Neumann R. J. Mol. Catal. A: Chem.  1999,  138:  315 
    Google Scholar
8

General Procedure for the Oxidation-Acyloxylation Reaction of 2-Arylpyridine 1 with Aldehydes 2
To a mixture of 2-arylpyridine (0.25 mmol), aldehyde (0.5 mmol), Cu(OAc)2 (10 mol%, 4.5 mg), and chlorobenzene (2 mL) was added tert-butyl hydroperoxide (2 equiv, 5.5 M in decane) dropwise at r.t. The reaction mixture was stirred at 135 ˚C for 24 h. After the reaction, EtOAc (10 mL) was added, and the mixture was washed with aq NaOH (1 M, 5 mL), H2O (10 mL), and brine (10 mL), respectively. The filtrate was dried over Na2SO4 and then concentrated in vacuo. The residue was purified by column chromatography (silica gel, PE-EtOAc as eluent) to afford the desired products 3a-n.

9

Unexpectedly, when toluene was employed under the optimal conditions, only a trace amount of benzoxylated product was obtained.