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;
Further Information

Publication History

Received 3 September 2009
Publication Date:
13 November 2009 (online)

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.

    References and Notes

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