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

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

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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): ν_max = 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.