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;
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Publikationsverlauf

Received 3 September 2009
Publikationsdatum:
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.

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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.