Subscribe to RSS
DOI: 10.1055/s-2006-947330
Formation of Isoxazoles Using Cerium Ammonium Nitrate (CAN): A One-Pot Synthesis of Glycomimetics
Publication History
Publication Date:
04 July 2006 (online)
![](https://www.thieme-connect.de/media/synlett/200611/lookinside/thumbnails/10.1055-s-2006-947330-1.jpg)
Abstract
1,3-Dipolar cycloaddition reactions of carbohydrate dipolarophiles with cerium(IV) ammonium nitrate CAN(IV) in acetone, acetophenone, or pinacolone yielded the corresponding 3,5-disubstituted isoxazoles, stable pharmacophores for glycomimetic syntheses.
Key words
carbohydrates - cycloadditions - heterocycles - isoxazoles - CAN(IV)
- 1
Compain P.Martin OR. Bioorg. Med. Chem. 2001, 9: 3077 -
2a
Stütz AE. Iminosugar as Glycosidase Inhibitors: Nojiromycin and Beyond Wiley-VCH; Weinheim: 1998. -
2b
Chapleur Y. Carbohydrate Mimics, Concepts and Methods Wiley-VCH; Weinheim: 1998. -
3a
Drinnan NB.Vari F. Mini Rev. Med. Chem. 2003, 3: 633 -
3b
Fügedi P. Mini Rev. Med. Chem. 2003, 3: 659 -
3c
Hurtley S.Service R.Szuromi P. Science 2001, 291: 2337 -
3d
Sears P.Wong CH. Angew. Chem. Int. Ed. 1999, 38: 2300 - 4
Silva MT.Tributino JL.Miranda AL.Barreiro EJ.Fraga CA. Eur. J. Med. Chem. 2002, 37: 163 - 5
Batra S.Roy AK.Patra A.Bhaduri AP.Surin WR.Ragharan SAV.Sharma P.Kapoor K.Dikshit M. Bioorg. Med. Chem. 2003, 11: 2269 - 6
Patra A.Batra S.Bhaduri AP.Khanna A.Chander R.Dikshit M. Bioorg. Med. Chem. 2004, 12: 2059 - 7
Conti P.Dallanoce C.De Amici M.De Micheli C.Klotz K.-N. Bioorg. Med. Chem. Lett. 1998, 6: 401 - 8
Shin KD.Lee M.-Y.Shin D.-S.Lee S.Son K.-H.Paik Y.-K.Kwon B.-M.Han DC. J. Biol. Chem. 2005, 280: 41439 -
9a
Zificsak CA.Hlasta DJ. Tetrahedron 2004, 60: 8991 -
9b
Fader LD.Carreira EM. Org. Lett. 2004, 6: 2485 -
9c
Bode JW.Fraefel N.Muri D.Carreira EM. Angew. Chem. Int. Ed. 2001, 40: 2082 -
10a
Gothelf KV.Jorgensen AK. Chem. Rev. 1998, 98: 863 -
10b
Carruthers W. Cycloaddition Reaction in Organic Synthesis Pergamon Press; Oxford UK: 1990. p.269 -
10c
Caramella P.Grunanger P. In 1,3-Dipolar Cycloaddition Chemistry Vol. 1:Padwa A. Wiley; New York: 1984. p.291 -
10d
Padwa A. 1,3-Dipolar Cycloaddition Chemistry Wiley; New York: 1984. -
11a
Torsell KBG. Nitrile Oxides, Nitrones and Nitronates in Organic Synthesis VCH; Weinheim: 1988. -
11b
Larsen KE.Torsell KBG. Tetrahedron 1984, 40: 2985 -
11c
Liu K.-C.Shelton BR.Howe RK. J. Org. Chem. 1980, 45: 3916 - 12
Maugein N.Wagner A.Mioskowski C. Tetrahedron Lett. 1997, 38: 1547 - 13
Mukaiyama T.Hoshino T. J. Am. Chem. Soc. 1960, 82: 5339 -
14a
DeShong P.Kell DA.Sidler DR. J. Org. Chem. 1985, 50: 2309 -
14b
DeShong P.Kell DA. Tetrahedron Lett. 1986, 27: 3979 -
14c
Mendez F.Tamariz J.Geerlings P. J. Phys. Chem. 1998, 102: 6292 - 15
Himo F.Lovell T.Hilgraf R.Rostovsev VV.Noodleman L.Sharpless BK.Folkin VV. J. Am. Chem. Soc. 2005, 127: 210 -
16a
Ganguly N.Sukai AK.De S. Synth. Commun. 2001, 31: 301 -
16b
Horiuchi CA.Ochiai K.Fukunishi H. Chem. Lett. 1994, 185 - 17
Wade PA.Amin NV.Yen H.-K.Price DT.Huhn GF. J. Org. Chem. 1984, 49: 4595 - 18
Moore JE.Davies MW.Goodenough KM.Wybrow RAJ.York M.Johnson CN.Harrity PA. Tetrahedron 2005, 61: 6707 -
19a
Roy R.Trono MC.Giguère D. In Glycomimetics - Modern Synthetic MethodologiesRoy R. ACS Symposium Series 896, American Chemical Society; Washington DC: 2005. p.137 -
19b
Baek M.-G.Roy R. Bioorg. Med. Chem. 2002, 10: 11 -
19c
Roy R.Das KS.Santoyo-Gonzalez F.Hernandez-Mateo F.Dam TK.Brewer CF. Chem. Eur. J. 2000, 6: 1757 -
19d
Roy R.Das SK.Dominique R.Trono MC.Hernandez-Mateo F.Santoyo-Gonzalez F. Pure Appl. Chem. 1999, 71: 565 - 20
Wamhoff H. In Comprehensive Heterocyclic Chemistry Vol. 4:Katritzky AR.Rees CW.Potts KT. Pergamon Press; Oxford: 1984. p.669 -
21a
Liu L.McKee M.Postema MHD. Curr. Org. Chem. 2005, 5: 1133 -
21b
Gallos JK.Koumbis AE. Curr. Org. Chem. 2003, 7: 397 -
21c
Kirsching A.Jesberger M.Schoning KU. Synthesis 2001, 507 -
21d
Berecibar A.Grandjean C.Siriwardena A. Chem. Rev. 1999, 99: 779 -
21e
Herczegh P.Kovacs I.Erdosi G.Varga T.Agocs A.Szilagyi L.Sztaricskai F.Berecibar A.Lukacs G.Olesker A. Pure Appl. Chem. 1997, 69: 519 -
21f
Ferrier RJ. Chem. Rev. 1993, 93: 2779 - 22
Itoh K.-i.Takahashi S.Ueki T.Sugiyama T.Takahashi TT.Horiuchi CA. Tetrahedron Lett. 2002, 43: 7035 - 23
Itoh K.-i.Horiushi CA. Tetrahedron 2004, 60: 1671 - 24
Siguyama T. Appl. Organomet. Chem. 1995, 9: 399 - 25
Nelson SD.Kasparian DJ.Trager WF. J. Org. Chem. 1972, 37: 2686 -
26a
Mitchell EP.Sabin C.Snajdrova L.Pokorna M.Perret S.Gautier C.Hofr C.Gilboa-Garber N.Koca J.Wimmerova M.Imberty A. Proteins: Struct. Funct. Bioinf. 2005, 58: 735 -
26b
Imberty A.Wimmerova M.Mitchell EP.Gilboa-Garber N. Microb. Infect. 2004, 6: 221 -
26c
Roussel P.Lamblin G. Adv. Exp. Med. Biol. 2003, 535: 17 -
26d
Mitchell EP.Houles C.Sudakevitz D.Wimmerova M.Gautier C.Perez S.Wu AM.Gilboa-Garber N.Imberty A. Nat. Struct. Biol. 2002, 9: 918 -
27a
Giguère D.Sato S.St-Pierre C.Sirois S.Roy R. Bioorg. Med. Chem. Lett. 2006, 16: 1668 -
27b
Ahmad N.Gabius H.-J.André S.Kaltner H.Sabesan S.Roy R.Liu B.Macaluso F.Brewer CF. J. Biol. Chem. 2004, 279: 10841 -
27c
André S.Liu B.Gabius H.-J.Roy R. Org. Biomol. Chem. 2003, 1: 3909 -
28a
Hsu DK.Liu FT. Glycoconjugate J. 2004, 19: 507 -
28b
Hermandes JD.Baum LG. Glycobiolology 2002, 12: 127R -
29a
Sato S.Nieminem J. Glycoconjugate J. 2004, 19: 441 -
29b
Liu FT. Int. Arch. Allergy Immunol. 2005, 136: 385 - 30
Ouellet M.Mercier S.Pelletier I.Bounou S.Roy J.Hirabayashi J.Sato S.Tremblay MJ. J. Immunol. 2005, 174: 4120 - 31
Giguère D.Patnam R.Bellefleur M.-A.St-Pierre C.Sato S.Roy R. Chem. Commun. 2006, 2379 -
32a
Bouckaert J.Berglund J.Shembri M.De Genst E.Cools L.Wuhrer M.Hung C.-S.Pinker J.Slättegard R.Zavialov A.Choudhury D.Langermann S.Hultgren SJ.Wyns L.Klemm P.Oscarson S.Knight SD.De Greve H. Mol. Microbiol. 2005, 55: 441 -
32b
Hung C.-S.Bouckaert J.Pinker J.Widberg C.DeFusco A.Auguste CG.Strouse R.Langermann S.Waksman G.Hultgren S. Mol. Microbiol. 2002, 44: 903 -
32c
Schilling JD.Mulvey MA.Hultgren SJ. J. Infect. Dis. 2001, 183: S36 - 33
Nagahori N.Lee RT.Nishimura S.-I.Pagé D.Roy R.Lee YC. ChemBioChem 2002, 3: 836
References and Notes
Typical Procedure for Isoxazole Synthesis Using CAN(IV).Method A, Neat Solvent.
A mixture of acetylenic glycosides (0.5 mmol), ammonium cerium(IV) nitrate (0.5 mmol), and 4 Å MS in acetone (0.1 M) was stirred at reflux under nitrogen during 16-66 h (Table
[2]
). The mixture was poured into a solution of aq NaHCO3 (2.0 mL) and filtered over a Celite® pad. The filtrate was washed with brine (2 × 2.0 mL) and extracted with CH2Cl2. The organic layer was then washed with brine (2 × 2.0 mL), dried over Na2SO4, and concentrated under reduced pressure. Pure isoxazoles were isolated as clear oil by column chromatography using a mixture of EtOAc and hexane.
Method B, Ketones in MeCN.
A mixture of acetylenic glycosides (0.0695 g, 0.2 mmol), ammonium cerium(IV) nitrate (0.348 g, 0.6 mmol), the appropriate ketone (2.0 mmol), and 4 Å MS in MeCN (3.5 mL) was stirred at reflux under nitrogen during 16-66 h. The mixture was poored into a solution of aq NaHCO3 (2.0 mL) and filtered over a Celite® pad. The filtrate was washed with brine (2 × 2.0 mL) and extracted with CH2Cl2. The organic layer was then washed with brine (2 × 2.0 mL), dried over Na2SO4, and concentrated under reduced pressure. Pure isoxazoles were isolated as clear oil by column chromatography using a mixture of EtOAc and hexane.
All new compounds gave satisfactory analytical and spectral data. Data for selected compounds are as follows.
Compound 1a: oil. 1H NMR (300 MHz, CDCl3): δ = 6.63 (s, 1 H), 5.34 (dd, 1 H, J = 3.3, 10.2 Hz), 5.30 (dd, 1 H, J = 1.1, 3.3 Hz), 5.16 (d, 1 H, J = 3.9 Hz), 5.13 (dd, 1 H, J = 10.2, 3.9 Hz), 4.75 (dq, 2 H, J = 13.7, 0.6 Hz), 4.17 (dq, 1 H, J = 1.1, 6.6 Hz), 2.65 (s, 3 H), 2.16, 2.08, 1.98 (3 s, 3 × 3 H), 1.13 (d, 3 H, J = 6.6 Hz). 13C NMR (300 MHz, CDCl3): δ = 191.7 (1 C), 170.5 (1 C), 170.0 (1 C), 169.7 (1 C), 161.9 (1 C), 118.4 (1 C), 101.9 (1 C), 96.2 (1 C), 70.8 (1 C), 67.7 (1 C), 67.6 (1 C), 65.0 (1 C), 60.3, (1 C), 27.2 (1 C), 20.7 (1 C), 20.6 (2 C), 15.7 (1 C). MS (ESI): m/z calcd for C18H23NO10Na: 436.13; found: 436.3 [M + Na+].
Compound 1b: oil. 1H NMR (300 MHz, CDCl3): δ = 8.29 (m, 2 H), 7.65 (m, 1 H), 7.52 (m, 2 H), 6.80 (s, 1 H, H-9), 5.38 (dd, 1 H, J = 3.3, 10.7 Hz), 5.32 (dd, 1 H, J = 1.1, 3.3 Hz), 5.21 (d, 1 H, J = 3.9 Hz), 5.15 (dd, 1 H, J = 10.7, 3.9 Hz), 4.81 (dq, 2 H, J = 13.7, 0.6 Hz), 4.21 (dq, 1 H, J = 1.1, 6.6 Hz), 2.17, 2.09, 1.99 (3 s, 3 × 3 H), 1.15 (d, 3 H, J = 6.6 Hz). 13C NMR (300 MHz, CDCl3): δ = 185.6 (1 C), 170.7 (1 C), 170.6 (1 C), 170.2 (1 C), 169.1 (1 C), 135.7 (1 C), 134.4 (1 C), 130.9 (1 C), 130.3 (1 C), 104.6 (1 C), 96.6 (1 C), 71.1 (1 C), 68.0 (1 C), 67.9 (1 C), 65.3 (1 C), 60.6, (1 C), 21.0 (1 C), 20.9 (2 C), 16.0 (1 C). MS (ESI): m/z calcd for C23H25NO10Na: 498.15; found: 498.3 [M + Na+].
Compound 1c: oil. 1H NMR (300 MHz, CDCl3): δ = 6.59 (s, 1 H), 5.34 (dd, 1 H, J = 3.3, 10.4 Hz), 5.29 (dd, 1 H, J = 1.1, 3.3 Hz), 5.16 (d, 1 H, J = 3.6 Hz), 5.12 (dd, 1 H, J = 10.4, 3.6 Hz), 4.74 (dq, 2 H, J = 13.7, 0.6 Hz), 4.17 (dq, 1 H, J = 1.1, 6.6 Hz), 2.15, 2.07, 1.97 (3 s, 3 × 3 H), 1.37, (s, 3 × 3 H), 1.11 (d, 3 H, J = 6.6 Hz). 13C NMR (300 MHz, CDCl3): δ = 199.4 (1 C), 170.4 (1 C), 170.3 (1 C), 169.8 (1 C), 168.2 (1 C), 160.4 (1 C), 104.0 (1 C), 96.3 (1 C), 70.8 (1 C), 67.7 (1 C), 67.6 (1 C), 65.0 (1 C), 60.3 (1 C), 44.6 (1 C), 26.5 (3 C), 20.6 (1 C), 20.5 (1 C), 20.4 (1 C), 15.7 (1 C). MS (ESI): m/z calcd for C21H29NO10Na: 478.18; found: 478.3 [M + Na+].
Compound 3a (Table
[2]
, entry 4): oil. 1H NMR (300 MHz, CDCl3): δ = 6.46 (s, 1 H), 5.25 (m, 3 H), 4.92 (d, 1 H, J = 1.8 Hz), 4.79 (d, 1 H, J = 12.4 Hz), 4.72 (d, 1 H, J = 12.4 Hz), 4.24 (dd, 1 H, J = 12.3, 5.4 Hz), 4.02 (m, 2 H), 2.62 (s, 3 H), 2.12, 2.08, 2.01, 1.98 (4 s, 4 × 3 H). 13C NMR (300 MHz, CDCl3): δ = 191.5 (1 C), 170.5 (1 C), 169.8 (1 C), 169.7 (1 C), 169.6 (1 C), 168.9 (1 C), 161.9 (1 C), 102.3 (1 C), 97.3 (1 C), 69.1 (1 C), 69.0 (1 C), 68.6 (1 C), 65.7 (1 C), 62.2 (1 C), 59.7 (1 C), 27.2 (1 C), 20.7 (1 C), 20.6 (2 C), 20.5 (1 C). MS (ESI): m/z calcd for C20H25NO12: 471.14; found: 472.1 [M + H+].
Compound 3b (Table
[2]
, entry 5): oil. 1H NMR (300 MHz, CDCl3): δ = 8.28 (d, 2 H, J = 8.2 Hz), 7.62 (1 H, t, J = 8.2 Hz), 7.53 (2 H, t, J = 8.2 Hz), 6.62 (s, 1 H), 5.30 (m, 3 H), 4.98 (d, 1 H, J = 1.8 Hz), 4.83 (d, 1 H, J = 12.4 Hz), 4.78 (d, 1 H, J = 12.4 Hz), 4.27 (m, 1 H), 4.05 (m, 2 H), 2.17, 2.10, 2.02, 1.99 (4 s, 4 × 3 H). 13C NMR (300 MHz, CDCl3): δ = 185.2 (1 C), 170.5 (1 C), 169.8 (1 C), 169.7 (1 C), 169.6 (1 C), 168.1 (1 C), 162.1 (1 C), 134.1 (1 C), 130.6 (1 C), 128.5 (1 C), 104.7 (1 C), 97.4 (1 C), 69.2 (1 C), 69.0 (1 C), 68.8 (1 C), 65.9 (1 C), 62.2 (1 C), 59.7 (1 C), 20.7 (1 C), 20.6 (2 C), 20.5 (1 C). MS (ESI): m/z calcd for C25H27NO12: 533.1; found: 534.1 [M + H+].