Highly Regioselective Synthesis of 2,3,5-Trisubstituted Furans via Phosphine-Catalyzed Ring-Opening Cycloisomerization Reactions of Cyclopropenyl Dicarboxylates

Abstract

Different 2,3,5-trisubstituted furans have been regioselectively synthesized through a ring-opening cycloisomerization of functionalized cyclopropenyl carboxylates with moderate to excellent yields by using tri(2-furanyl)phosphine as the catalyst.

Key words

furans - regioselectivity - ring-opening cycloisomerization - cyclopropenes - tri(2-furanyl)phosphine

References and Notes

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15

Representative Procedure for the Synthesis of 2-Methoxy-3-methoxycarbonyl-5-butylfuran (2a) in a 5.0 mmol Scale
To a Schlenk reaction tube with a screw cap, evacuated and backfilled with argon, were added sequentially (2-furanyl)₃P (116 mg, 0.50 mmol), cyclopropenyl dicarboxylate 1a (1.058 g, 4.99 mmol), and toluene (50 mL). The resulting mixture was refluxed at 150 ˚C. After 18 h the reaction was over (monitored by TLC). Evaporation and column chromatography on silica gel (eluent: PE-EtOAc = 20:1) afforded the desired product 2a ^9o (1.005 g, 95% yield); oil. ^¹H NMR (400 MHz, CDCl₃): δ = 6.15 (t, J = 1.0 Hz, 1 H, CH=), 4.05 (s, 3 H, CO₂CH₃), 3.76 (s, 3 H, OCH₃), 2.47 (td, J = 7.4, 0.8 Hz, 2 H, =CCH₂), 1.60-1.50 (m, 2 H, CH₂), 1.40-1.29 (m, 2 H, CH₂), 0.90 (t, J = 7.4 Hz, 3 H, CH₃). ^¹³C NMR (100 MHz, CDCl₃): δ = 163.6, 161.0, 146.0, 105.8, 91.2, 57.9, 51.0, 29.5, 27.1, 22.0, 13.7. MS (EI): m/z = 212 (19.03) [M⁺], 169 (100) [M⁺ - C₃H₇]. IR (neat): 2955, 2873, 1720, 1607, 1470, 1407, 1278, 1212, 1191, 1138, 1088 cm^-¹.