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

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Synlett 2010(5): 777-781
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;

Further Information

Publication History

Received 30 November 2009
Publication Date:
19 January 2010 (online)

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

References and Notes

1a Carlsen L. Dopp D. Dopp H. Duus F. Hartman H. Lang-Fugmann S. Schulze B. Smalley RK. Wakefield BJ. In Houben-Weyl Methods of Organic Chemistry Vol. E8a: Schaumann E. Georg Thieme Verlag; Stuttgart, Germany: 1992. p.45-204

Google Scholar
1b Sperry J. Wright D. Curr. Opin. Drug Discovery Dev. 2005, 8: 723

Google Scholar
2a Daidone G. Raffa D. Maggio B. Plescia F. Cutuli VMC. Mangano NG. Caruso A. Arch. Pharm. Pharm. Med. Chem. 1999, 332: 50

Google Scholar
2b Tomita K. Takahi Y. Ishizuka R. Kamamura S. Nakagawa M. Ando M. Nakanishi T. Nakamura T. Udaira H. Ann. Sankyo Res. Lab. 1973, 1: 25; Chem. Abstr. 1974, 80, 120808

Google Scholar
2c Talley JJ. Prog. Med. Chem. 1999, 13: 201

Google Scholar
2d Talley JJ. Brown DL. Carter JS. Graneto MJ. Koboldt CM. Masferrer JL. Perkins WE. Rogers RS. Shaffer AF. Zhang YY. Zweifel BS. Seibert K. J. Med. Chem. 2000, 43: 775

Google Scholar
2e Giovannoni MP. Vergelli C. Ghelardini C. Galeotti N. Bartolini A. Kal Piaz V.
J. Med. Chem. 2003, 46: 1055

Google Scholar
2f Li W.-T. Hwang D.-R. Chen C.-P. Shen C.-W. Huang C.-L. Chen T.-W. Lin C.-H. Chang Y.-L. Chang Y.-Y. Lo Y.-K. Tseng H.-Y. Lin C.-C. Song J.-S. Chen H.-C. Chen S.-J. Wu S.-H. Chen C.-T. J. Med. Chem. 2003, 46: 1706

Google Scholar
3a Roy AK. Rajaraman B. Batra S. Tetrahedron 2004, 60: 2301

Google Scholar
3b Wankhede KS. Vaidya VV. Sarang PS. Salunkhe MM. Trivedi GK. Tetrahedron Lett. 2008, 49: 2069

Google Scholar
4a Takenaka K. Nakatsuka S. Tsujihara T. Koranne PS. Sasai H. Tetrahedron: Asymmetry 2008, 19: 2492

Google Scholar
4b Koranne PS. Tsujihara T. Arai MA. Bajracharya GB. Suzuki T., Onitsuka K., Sasai H. Tetrahedron: Asymmetry 2007, 18: 919

Google Scholar
5a Tanaka M. Haino T. Ideta K. Kubo K. Mori A. Fukazawa Y. Tetrahedron 2007, 63: 652

Google Scholar
5b Tanaka M. Haino T. Ideta K. Kubo K. Mori A. Fukazawa Y. Tetrahedron Lett. 2004, 45: 2277

Google Scholar
5c Vieira AA. Bryk FR. Conte G. Bortoluzzi AJ. Gallardo H. Tetrahedron Lett. 2009, 50: 905

Google Scholar
6a Wakefield BJ. In Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 11: Shaumann E. Georg Thieme Verlag; Stuttgart: 2001. p.229-288

Google Scholar
6b Pinho e Melo TMVD. Curr. Org. Chem. 2005, 9: 925

Google Scholar
6c Jager V. Colinas PA. In Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products Vol. 59: Padwa A. Wiley; Hoboken: 2002. p.361-472

Google Scholar
7a Tang S. He J. Sun Y. He L. She X. Org. Lett. 2009, 11: 3982

Google Scholar
7b Bourbeau MP. Rider JT. Org. Lett. 2006, 8: 3679

Google Scholar
7c Waldo JP. Larock RC. Org. Lett. 2005, 7: 5203

Google Scholar
7d Waldo JP. Larock RC. J. Org. Chem. 2007, 72: 9643

Google Scholar
7e Hansen TV. Wu P. Fokin VV. J. Org. Chem. 2005, 70: 7761

Google Scholar
7f Girardin M. Alsabeh PG. Lauzon S. Dolman SJ. Ouellet SG. Hughes G. Org. Lett. 2009, 11: 1159

Google Scholar
7g Lautens M. Roy A. Org. Lett. 2000, 2: 555

Google Scholar
7h Wang K. Xiang D. Liu J. Pan W. Dong D. Org. Lett. 2008, 10: 1691

Google Scholar
7i Himo F. Lovell T. Hilgraf R. Rostovtsev VV. Noodleman L. Sharpless KB. Fokin VV. J. Am. Chem. Soc. 2005, 127: 210

Google Scholar
7j Grecian S. Fokin VV. Angew. Chem. Int. Ed. 2008, 47: 8285

Google Scholar
7k Xu JP. Hamme AT. Synlett 2008, 0919

Google Scholar
For reviews of gold-catalyzed organic reactions, see:
8a Hashmi ASK. Hutchings GJ. Angew. Chem. Int. Ed. 2006, 45: 7896

Google Scholar
8b Hashmi ASK. Chem. Rev. 2007, 107: 3180

Google Scholar
8c Amijs CHM. Ferrer C. Echavarren AM. Chem. Commun. 2007, 698

Google Scholar
8d Fürstner A. Davies PW. Angew. Chem. Int. Ed. 2006, 46: 3410

Google Scholar
8e Hoffmann-Roder A. Krause N. Org. Biomol. Chem. 2005, 3: 387

Google Scholar
8f Hashmi ASK. Angew. Chem. Int. Ed. 2005, 44, 6990 ; Angew. Chem. 2005, 117, 7150

Google Scholar
8g Núñez EJ. Echavarren AM. Chem. Commun. 2007, 333

Google Scholar
8h Widenhoefer RA. Han X. Eur. J. Org. Chem. 2006, 4555

Google Scholar
8i Shen HC. Tetrahedron 2008, 64: 7847

Google Scholar
8j Shen HC. Tetrahedron 2008, 64: 3885

Google Scholar
8k Li Z. Brouwer C. He C. Chem. Rev. 2008, 108: 3289

Google Scholar
8l Wang M.-Z. Wong M.-K. Che C.-M. Chem. Eur. J. 2008, 14: 8353

Google Scholar
8m Ferrer C. Amijs CHM. Echavarren AM. Chem. Eur. J. 2008, 14: 8353

Google Scholar
8n Gorin DJ. Toste D. Nature 2007, 446: 395

Google Scholar
8o Asao N. Synlett 2006, 1645

Google Scholar
8p Ma S. Yu S. Gu Z. Angew. Chem. Int. Ed. 2006, 45: 200

Google Scholar
8q Echavarren AM. Nevado C. Chem. Soc. Rev. 2004, 33: 431

Google Scholar
8r Dyker G. Angew. Chem. Int. Ed. 2000, 39: 4237

Google Scholar
8s Hashmi ASK. Gold Bull. 2004, 37: 51

Google Scholar
8t Ishida T. Haruta M. Angew. Chem. Int. Ed. 2007, 46: 7154

Google Scholar
8u Skouta R. Li C.-J. Tetrahedron 2008, 64: 4917

Google Scholar
9 Hashmi ASK. Schwarz L. Choi J.-H. Frost TM. Angew. Chem. Int. Ed. 2000, 39: 2285 ; Angew. Chem. 2000, 112, 2382

Crossref PubMed Google Scholar
10a Debleds O. Zotto CD. Vrancken E. Campagne J.-M. Retaileau E. Adv. Synth. Catal. 2009, 351: 1991

Google Scholar
10b Winter C. Krause N. Angew. Chem. Int. Ed. 2009, 48: 6339

Google Scholar
10c Yeom H.-S. Lee E.-S. Shin S. Synlett 2007, 2292

Google Scholar
11a Weyrauch JP. Hashmi ASK. Schuster A. Hengst T. Schetter S. Littmann A. Rudolph M. Hamzic M. Visus J. Rominger F. Frey W. Bats JW. Chem. Eur. J. 2009, DOI: 10.1002/chem.200902472

Google Scholar
11b Hashmi ASK. Rudolph M. Schymura S. Visus J. Frey W. Eur. J. Org. Chem. 2006, 4905

Google Scholar
11c Hashmi ASK. Salathé R. Frey W. Synlett 2007, 1763

Google Scholar
11d Hashmi ASK. Weyruch JP. Schymura W. Bats JW. Org. Lett. 2004, 6: 4391

Google Scholar
12a Praveen C. Sagayaraj YW. Perumal PT. Tetrahedron Lett. 2009, 50: 644

Google Scholar
12b Praveen C. Kiruthiga P. Perumal PT. Synlett 2009, 1990

Google Scholar
12c Praveen C. Jegatheesan S. Perumal PT. Synlett 2009, 2795

Google Scholar
12d Praveen C. Karthikeyan K. Perumal PT. Tetrahedron 2009, 65: 9244

Google Scholar
13 Short KM. Ziegler CBJr. Tetrahedron Lett. 1993, 34: 75

Crossref Google Scholar
14a Tohda Y. Sonogashira K. Hagihara N. Synthesis 1977, 1977

Google Scholar
14b Lin C.-F. Lu W.-D. Wang I.-W. Wu M.-J. Synlett 2003, 2057

Google Scholar
14c Kobayashi T. Tanaka M. J. Chem. Soc., Chem. Commun. 1981, 333

Google Scholar
14d Mohamed Ahmed MS. Mori A. Org. Lett. 2003, 5: 3057

Google Scholar
14e Birkofer L. Ritter A. Uhlenbrauck H. Chem. Ber. 1963, 96: 3280

Google Scholar

15

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.