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Synlett 2011(7): 931-934  
DOI: 10.1055/s-0030-1259904
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Jie Chena, Shengjun Nia, Shengming Ma*a,b
a State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. of China
b Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal University, 3663 North Zhongshan Road, Shanghai 200062, P. R. of China
Fax: +86(21)62609305; e-Mail: masm@sioc.ac.cn;
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Publication History

Received 3 December 2010
Publication Date:
10 March 2011 (online)

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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

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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.