PDF herunterladen
Synlett 2009(20): 3295-3298  
DOI: 10.1055/s-0029-1218367
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

DABCO-Induced [2+2+2]-Cycloaddition Reaction of Ethyl Propiolate and Aryl Aldehydes for the Synthesis of 4-Aryl-4H-pyrans

Weibing Liu, Huanfeng Jiang*, Peng Zhou, Shifa Zhu
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, P. R. of China
Fax: +86(20)87112906; e-Mail: jianghf@scut.edu.cn;
Weitere Informationen

Publikationsverlauf

Received 3 September 2009
Publikationsdatum:
13. November 2009 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

The first DABCO-induced [2+2+2]-cycloaddition reaction of ethyl propiolate and aryl aldehydes is reported for selectively constructing 4-aryl-4H-pyrans in moderate to good yields.

Key words

DABCO - [2+2+2]-cycloaddition reaction - ethyl propiolate - aldehydes - 4-aryl-4H-pyrans

    References and Notes

  • 1a Walji AM. MacMillan DWC. Synlett  2007,  1477 
    Google Scholar
  • 1b Tietze LF. Haunert F. Stimulating Concepts in Chemistry   Wiley; New York: 2000. 
    Google Scholar
  • 1c Wender PA. Miller BL. In Organic Synthesis: Theory and Applications   Vol. 2:  Hudlicky T. JAI Press; Greenwich CT: 1993.  p.27 
    Google Scholar
  • 2a Müller TJJ. Metal Catalyzed Cascade Reactions, In Topics in Organometallic Chemistry   Vol. 19:  Springer; New York: 2006. 
    Google Scholar
  • 2b Hayashi T. Yamasaki K. Chem. Rev.  2003,  103:  2829 
    Google Scholar
  • 2c Naodovic M. Yamamoto H. Chem. Rev.  2008,  108:  3132 
    Google Scholar
  • 2d Paull DH. Abraham CJ. Scerba MT. Alden DE. Lectka T. Acc. Chem. Res.  2008,  41:  655 
    Google Scholar
  • 2e Terao J. Kambe N. Acc. Chem. Res.  2008,  41:  1545 
    Google Scholar
  • 2f Patil NT. Yamamoto Y. Chem. Rev.  2008,  108:  3395 
    Google Scholar
  • 3a Enders D. Grondal C. Huttl MRM. Angew. Chem. Int. Ed.  2007,  46:  1570 
    Google Scholar
  • 3b Johnson AW. Tebby JC. J. Chem. Soc.  1961,  2126 
    Google Scholar
  • 3c Tebby JC. Wilson IF. Grifiths DV. J. Chem. Soc., Perkin Trans. 1  1979,  2133 
    Google Scholar
  • 3d Diels O. Alder K. Liebigs Ann. Chem.  1932,  498:  16 
    Google Scholar
  • 3e Acheson RM. Adv. Heterocycl. Chem.  1963,  1:  125 
    Google Scholar
  • 3f Yu XZ. Ren HJ. Xiao YJ. Zhang JL. Chem. Eur. J.  2008,  14:  8481 
    Google Scholar
  • 4a Zhu S. Hudson TH. Kyle DE. Lin AJ. J. Med. Chem.  2002,  45:  3491 
    Google Scholar
  • 4b Chung YM. Gong JH. Kim TH. Kim JN. Tetrahedron Lett.  2001,  42:  9023 
    Google Scholar
  • 4c Ciclosi M. Fava C. Galeazzi R. Orena M. Sepulveda-Arques J. Tetrahedron Lett.  2002,  43:  2199 
    Google Scholar
  • 4d Kim JN. Lee HJ. Lee KY. Gong JH. Synlett  2002,  173 
    Google Scholar
  • 4e Gong JH. Kim HR. Ryu EK. Kim JN. Bull. Korean Chem. Soc.  2002,  23:  789 
    Google Scholar
  • 4f Lawrence NJ. Crump JP. McGown AT. Hadfield JA. Tetrahedron Lett.  2001,  42:  3939 
    Google Scholar
  • 4g Yadav JS. Subba Reddy BV. Geetha V. Synlett  2002,  513 
    Google Scholar
  • 4h Wang B. Yu X.-M. Lin G.-Q. Synlett  2001,  904 ; special issue
    Google Scholar
  • 4i Rose PM. Clifford AA. Rayner CM. Chem. Commun.  2002,  968 
    Google Scholar
  • 4j Gawronski J. Wascinska N. Gajewy J. Chem. Rev.  2008,  108:  5227 
    Google Scholar
  • 4k Brandi A. Cicchi S. Cordero FM. Chem. Rev.  2008,  108:  3988 
    Google Scholar
  • 4l Meng XT. Huang Y. Chen RY. Org. Lett.  2009,  11:  137 
    Google Scholar
  • 5a Gonzalez R. Martin N. Seoane C. Tetrahedron Lett.  1992,  33:  3809 
    Google Scholar
  • 5b Shestopalov AM. Niazimbetova DH. Heterocycles  1999,  51:  1101 
    Google Scholar
  • 6a Mulwad VV. Shirodkar JM. Indian J. Heterocycl. Chem.  2002,  11:  199 
    Google Scholar
  • 6b Mulwad VV. Pawar RB. Indian J. Heterocycl. Chem.  2001,  10:  241 
    Google Scholar
  • 6c Lei YJ. Yang YZ. Liu H. Zhu CH. Chin. J. Med. Chem.  2001,  11:  270 
    Google Scholar
  • 6d Kortenska VD. Velikova MP. Yanishlieva NV. Totzeva IR. Bankova VS. Marcucci MC. Eur. J. Lipid. Sci. Technol.  2002,  104:  19 
    Google Scholar
  • 6e Longobardi M. Mariani E. Bargagna A. Mazzeo F. Vitelli MR. Giordano L. Falcone G. Farmaco  2001,  56:  625 
    Google Scholar
  • 6f Horino H. Mimura T. Kagechika K. Ohta M. Kubo H. Kitagawa M. Chem. Pharm. Bull.  1998,  46:  602 
    Google Scholar
  • 6g Manolov L. Danchev ND. Arch. Pharm.  2003,  336:  83 
    Google Scholar
  • 6h Shafae AM. Ibrahim MA. Pharmazie  2003,  58:  143 
    Google Scholar
  • 6i Wu JY. Fong WF. Zhang JX. Leung CH. Kwong HL. Meng S. Li D. Chenug HY. Eur. J. Pharm.  2003,  473:  9 
    Google Scholar
  • 6j Yong J. Zhao YF. Still CC. Sacalis JN. Tsinghua Sci. Technol.  2000,  5:  159 
    Google Scholar
  • 6k Ahluwalia VK. Kaila N. Bala S. Indian. J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.  1987,  26:  700 
    Google Scholar
  • 6l Mail RS. Joshi PP. Sandhu PK. Manekar-Tilve A. J. Chem. Soc., Perkin Trans. 1  2002,  371 
    Google Scholar
  • 6m Magiatis P. Melliou E. Skaltsounis AL. Mitaku S. Leonce S. Reard P. Pierre A. Atassi G. J. Nat. Prod.  1998,  61:  982 
    Google Scholar
  • 6n Madkour HMF. Mahmoud MR. Sakr AM. Habashy MM. Sci. Pharm.  2001,  69:  33 
    Google Scholar
  • 6o Jolivet C. Rivalle C. Bisagni E. Heterocycles  1996,  43:  995 
    Google Scholar
  • 6p Marco JL. Delos RC. Carreiras MC. Banos JE. Badia A. Vivas NM. Bioorg. Med. Chem.  2001,  9:  727 
    Google Scholar
  • 6q Bloxhem J. Dell CP. Smith CW. Heterocycles  1994,  38:  399 
    Google Scholar
  • 9 Nair V. Sreekanth AR. Vinod AU. Org. Lett.  2001,  3:  3495 
    CrossrefGoogle Scholar
7

The HMQC spectrum of diethyl 4-(3-nitrophenyl)-4H-pyran-3,5-dicarboxylate enabled assignment of the directly bonded C-H moieties. The results showed that H-C correlations signals were 1.15-1.22/14.0, 4.01-4.13/60.9, 4.78/35.6, 7.41-7.45/128.9, 7.62/148.7, 7.68-7.70/135.1, 8.03-8.12/122.1 and 8.12/123.6, respectively.

8

Typical Procedure for the Cascade Reaction of Ethyl Propiolate with Benzaldehyde To a stirring mixture of ethyl propiolate (98 mg, 1 mmol) and benzaldehyde (53 mg, 0.5 mmol) in a round-bottom flask, 1,4-dioxane (6 mL), and DABCO (0.56 mg, 0.005 mmol) were added successively, and then the mixture was stirred at 90 ˚C for 12 h. After the reaction accomplished, the solvent was diluted with H2O and extracted with Et2O. The ether layer was washed with sat. salt water, and dried with anhyd MgSO4. The resulting mixture was then analyzed by GC and GC-MS. Volatiles were removed under reduced pressure, and the crude product was subjected to isolation by PTLC (GF254), eluted with a PE-Et2O (10:1) mixture to afford the desired product diethyl 4-phenyl-4H-pyran-3,5-dicarboxylate(3a). Colorless viscous oil. IR (KBr): νmax = 1713, 1655, 1616, 1475, 1248, 1178, 1077, 894, 695 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.56 (s, 2 H), 7.22 (m, 5 H), 4.65 (s, 1 H), 4.06 (m, 4 H), 1.17 (m, 6 H) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 165.5, 148.0, 143.7, 128.7, 128.1, 126.9, 112.9, 60.6, 35.7, 14.0 ppm. GC-MS: m/z (%) = 302.07 (27) [M+], 225.00(100). Anal. Calcd for C17H18O5: C, 67.54; H, 6.00. Found: C, 67.52; H, 6.03.