RSS-Feed abonnieren
DOI: 10.1055/s-0029-1219342
Gold(III)-Catalyzed Synthesis of Isoxazoles by Cycloisomerization of α,β-Acetylenic Oximes
Publikationsverlauf
Publikationsdatum:
19. Januar 2010 (online)
![](https://www.thieme-connect.de/media/synlett/201005/lookinside/thumbnails/10.1055-s-0029-1219342-1.jpg)
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
-
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 -
1b
Sperry J.Wright D. Curr. Opin. Drug Discovery Dev. 2005, 8: 723 -
2a
Daidone G.Raffa D.Maggio B.Plescia F.Cutuli VMC.Mangano NG.Caruso A. Arch. Pharm. Pharm. Med. Chem. 1999, 332: 50 -
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 -
2c
Talley JJ. Prog. Med. Chem. 1999, 13: 201 -
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 -
2e
Giovannoni MP.Vergelli C.Ghelardini C.Galeotti N.Bartolini A.Kal Piaz V.
J. Med. Chem. 2003, 46: 1055 -
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 -
3a
Roy AK.Rajaraman B.Batra S. Tetrahedron 2004, 60: 2301 -
3b
Wankhede KS.Vaidya VV.Sarang PS.Salunkhe MM.Trivedi GK. Tetrahedron Lett. 2008, 49: 2069 -
4a
Takenaka K.Nakatsuka S.Tsujihara T.Koranne PS.Sasai H. Tetrahedron: Asymmetry 2008, 19: 2492 -
4b
Koranne PS.Tsujihara T.Arai MA.Bajracharya GB. Suzuki T., Onitsuka K., Sasai H. Tetrahedron: Asymmetry 2007, 18: 919 -
5a
Tanaka M.Haino T.Ideta K.Kubo K.Mori A.Fukazawa Y. Tetrahedron 2007, 63: 652 -
5b
Tanaka M.Haino T.Ideta K.Kubo K.Mori A.Fukazawa Y. Tetrahedron Lett. 2004, 45: 2277 -
5c
Vieira AA.Bryk FR.Conte G.Bortoluzzi AJ.Gallardo H. Tetrahedron Lett. 2009, 50: 905 -
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 -
6b
Pinho e Melo TMVD. Curr. Org. Chem. 2005, 9: 925 -
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 -
7a
Tang S.He J.Sun Y.He L.She X. Org. Lett. 2009, 11: 3982 -
7b
Bourbeau MP.Rider JT. Org. Lett. 2006, 8: 3679 -
7c
Waldo JP.Larock RC. Org. Lett. 2005, 7: 5203 -
7d
Waldo JP.Larock RC. J. Org. Chem. 2007, 72: 9643 -
7e
Hansen TV.Wu P.Fokin VV. J. Org. Chem. 2005, 70: 7761 -
7f
Girardin M.Alsabeh PG.Lauzon S.Dolman SJ.Ouellet SG.Hughes G. Org. Lett. 2009, 11: 1159 -
7g
Lautens M.Roy A. Org. Lett. 2000, 2: 555 -
7h
Wang K.Xiang D.Liu J.Pan W.Dong D. Org. Lett. 2008, 10: 1691 -
7i
Himo F.Lovell T.Hilgraf R.Rostovtsev VV.Noodleman L.Sharpless KB.Fokin VV. J. Am. Chem. Soc. 2005, 127: 210 -
7j
Grecian S.Fokin VV. Angew. Chem. Int. Ed. 2008, 47: 8285 -
7k
Xu JP.Hamme AT. Synlett 2008, 0919 - For reviews of gold-catalyzed organic reactions, see:
-
8a
Hashmi ASK.Hutchings GJ. Angew. Chem. Int. Ed. 2006, 45: 7896 -
8b
Hashmi ASK. Chem. Rev. 2007, 107: 3180 -
8c
Amijs CHM.Ferrer C.Echavarren AM. Chem. Commun. 2007, 698 -
8d
Fürstner A.Davies PW. Angew. Chem. Int. Ed. 2006, 46: 3410 -
8e
Hoffmann-Roder A.Krause N. Org. Biomol. Chem. 2005, 3: 387 -
8f
Hashmi ASK. Angew. Chem. Int. Ed. 2005, 44, 6990 ; Angew. Chem. 2005, 117, 7150 -
8g
Núñez EJ.Echavarren AM. Chem. Commun. 2007, 333 -
8h
Widenhoefer RA.Han X. Eur. J. Org. Chem. 2006, 4555 -
8i
Shen HC. Tetrahedron 2008, 64: 7847 -
8j
Shen HC. Tetrahedron 2008, 64: 3885 -
8k
Li Z.Brouwer C.He C. Chem. Rev. 2008, 108: 3289 -
8l
Wang M.-Z.Wong M.-K.Che C.-M. Chem. Eur. J. 2008, 14: 8353 -
8m
Ferrer C.Amijs CHM.Echavarren AM. Chem. Eur. J. 2008, 14: 8353 -
8n
Gorin DJ.Toste D. Nature 2007, 446: 395 -
8o
Asao N. Synlett 2006, 1645 -
8p
Ma S.Yu S.Gu Z. Angew. Chem. Int. Ed. 2006, 45: 200 -
8q
Echavarren AM.Nevado C. Chem. Soc. Rev. 2004, 33: 431 -
8r
Dyker G. Angew. Chem. Int. Ed. 2000, 39: 4237 -
8s
Hashmi ASK. Gold Bull. 2004, 37: 51 -
8t
Ishida T.Haruta M. Angew. Chem. Int. Ed. 2007, 46: 7154 -
8u
Skouta R.Li C.-J. Tetrahedron 2008, 64: 4917 - 9
Hashmi ASK.Schwarz L.Choi J.-H.Frost TM. Angew. Chem. Int. Ed. 2000, 39: 2285 ; Angew. Chem. 2000, 112, 2382 -
10a
Debleds O.Zotto CD.Vrancken E.Campagne J.-M.Retaileau E. Adv. Synth. Catal. 2009, 351: 1991 -
10b
Winter C.Krause N. Angew. Chem. Int. Ed. 2009, 48: 6339 -
10c
Yeom H.-S.Lee E.-S.Shin S. Synlett 2007, 2292 -
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 -
11b
Hashmi ASK.Rudolph M.Schymura S.Visus J.Frey W. Eur. J. Org. Chem. 2006, 4905 -
11c
Hashmi ASK.Salathé R.Frey W. Synlett 2007, 1763 -
11d
Hashmi ASK.Weyruch JP.Schymura W.Bats JW. Org. Lett. 2004, 6: 4391 -
12a
Praveen C.Sagayaraj YW.Perumal PT. Tetrahedron Lett. 2009, 50: 644 -
12b
Praveen C.Kiruthiga P.Perumal PT. Synlett 2009, 1990 -
12c
Praveen C.Jegatheesan S.Perumal PT. Synlett 2009, 2795 -
12d
Praveen C.Karthikeyan K.Perumal PT. Tetrahedron 2009, 65: 9244 - 13
Short KM.Ziegler CBJr. Tetrahedron Lett. 1993, 34: 75 -
14a
Tohda Y.Sonogashira K.Hagihara N. Synthesis 1977, 1977 -
14b
Lin C.-F.Lu W.-D.Wang I.-W.Wu M.-J. Synlett 2003, 2057 -
14c
Kobayashi T.Tanaka M. J. Chem. Soc., Chem. Commun. 1981, 333 -
14d
Mohamed Ahmed MS.Mori A. Org. Lett. 2003, 5: 3057 -
14e
Birkofer L.Ritter A.Uhlenbrauck H. Chem. Ber. 1963, 96: 3280
References and Notes
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.