Gold(III)-Catalyzed Synthesis
of Isoxazoles by Cycloisomerization of α,β-Acetylenic
Oximes

C. Praveen; A. Kalyanasundaram; P. T. Perumal

doi:10.1055/s-0029-1219342

LETTER

Gold(III)-Catalyzed Synthesis of Isoxazoles by Cycloisomerization of α,β-Acetylenic Oximes

C. Praveen, A. Kalyanasundaram, P. T. Perumal*
Organic Chemistry Division, Central Leather Research Institute, Adyar, Chennai 600 020, India
Fax: +91(44)24911589; e-Mail: ptperumal@gmail.com;

Abstract

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Abstract

Cycloisomerization of α,β-acetylenic oximes leading to substituted isoxazoles was achieved using AuCl₃ as catalyst, under moderate reaction conditions. The reaction can be applied to various acetylenic oximes and gives good to excellent yields. The methodology is amenable for the selective synthesis of 3-substituted, 5-substituted or 3,5-disubstituted isoxazoles by simply altering the substituents on the acetylenic oximes.

Key words

α,β-acetylenic oximes - gold(III) chloride - cycloisomerization - isoxazoles

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References and Notes

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Synthesis of 3-Methyl-5-trimethylsilylisoxazole (3); Typical Procedure: To a solution of oxime 2n (500 mg, 3.22 mmol) in anhydrous CH₂Cl₂, was added AuCl₃ (9.76 mg, 0.0321 mmol) under an N₂ atmosphere and the solution was stirred for the specified time (Table [²] ) at 30 ˚C. After completion of the reaction (as indicated by TLC), the reaction mixture was concentrated under reduced pressure and purified by column chromatography over silica gel (100-200 mesh) to afford pure product, 3-methyl-5-trimethylsilylisoxazole (3n) as a yellow oil; IR (neat): 3302, 2912, 1604, 1419, 1338, 1085, 885, 757 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 0.29 [s, 9 H, Si(CH ₃)₃], 2.29 (s, 3 H, CH₃), 6.24 (s, 1 H, isoxazolinyl-H). ^¹³C NMR (125 MHz, CDCl₃): δ = -1.8, 10.8, 113.5, 157.7, 177.8. MS (EI): m/z = 172 [M]⁺. Anal. Calcd for C₇H₁₃NOSi: C, 54.15; H, 8.44; N, 9.02. Found: C, 53.95; H, 8.47; N, 9.15.