Synthesis of Isoxazolidinyl Epoxides by Oxone Treatment of 2,3-Dihydroisoxazoles in Acetone–Water Solution: A New Stereoselective Approach to Hydroxy-Substituted Isoxazolidines

Ondrej Záborský; Radka Štadániová; Jana Doháňošová; Ján Moncol; Róbert Fischer

doi:10.1055/s-0036-1590924

Synthesis, Table of Contents

Synthesis 2017; 49(22): 4942-4954
DOI: 10.1055/s-0036-1590924

feature

Synthesis of Isoxazolidinyl Epoxides by Oxone Treatment of 2,3-Dihydroisoxazoles in Acetone–Water Solution: A New Stereoselective Approach to Hydroxy-Substituted Isoxazolidines

Ondrej Záborský

^aInstitute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology in Bratislava, Radlinského 9, 81237 Bratislava, Slovak Republic Email: robert.fischer@stuba.sk

,

Radka Štadániová

^aInstitute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology in Bratislava, Radlinského 9, 81237 Bratislava, Slovak Republic Email: robert.fischer@stuba.sk

,

Jana Doháňošová

^bCentral Laboratories, Slovak University of Technology in Bratislava, Radlinského 9, 812 37 Bratislava, Slovak Republic

,

Ján Moncol

^cInstitute of Inorganic Chemistry, Technology and Materials, Slovak University of Technology in Bratislava, Radlinského 9, 81237 Bratislava, Slovak Republic

,

Róbert Fischer*

^aInstitute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology in Bratislava, Radlinského 9, 81237 Bratislava, Slovak Republic Email: robert.fischer@stuba.sk

› Author Affiliations

Abstract

All articles of this category

Abstract

A practical and efficient synthesis of new class of isoxazolidinyl epoxides by direct treatment of 4,5-unsubstituted 2,3-dihydroisoxazoles with Oxone and NaHCO₃ in acetone/water solution is described. All epoxidation reactions proceed with excellent anti-selectivity and provide stable products in very good yields. A concept for the development of stereoselective approach to 3,4-trans-hydroxy-substituted isoxazolidines, namely triazole derivatives as important molecules in medicinal chemistry is presented. The synthesis is characterized by highly syn-stereoselective conversion of epoxides to anomeric bromoisoxazolidines, which are found to be powerful reaction intermediates for the coupling reactions with various nucleophiles.

Key words

heterocycles - isoxazolidines - epoxides - triazoles - diastereoselectivity - aza-Michael addition - organocatalysis

Full Text

References

References

For selected reviews and papers on the isoxazolidines as intermediates in natural products synthesis, see:

1a Robertson J. Stevens K. Nat. Prod. Rep. 2017; 34: 62
1b Brandi A. Cardona F. Cicchi S. Cordero FM. Goti A. Chem. Eur. J. 2009; 15: 7808
1c Gothelf KV. Jørgensen KA. Chem. Rev. 1998; 98: 863
1d Parsons PJ. Penkett CS. Shell AJ. Chem. Rev. 1996; 96: 195

For selected reviews and papers on the use of isoxazolidines in the pharmaceutical research, see:

2a Berthet M. Cheviet T. Dujardin G. Parrot I. Martinez J. Chem. Rev. 2016; 116: 15235
2b Chiacchio MA. Giofré SV. Romeo R. Romeo G. Chiacchio U. Curr. Org. Synth. 2016; 13: 726
2c Chen H. Wang Z. Zhang Y. Huang Y. J. Org. Chem. 2013; 78: 3503
2d Chakraborty B. Samanta A. Sharma PK. Chhetri MS. Kafley S. Banerjee A. Sinha C. J. Chem. Pharm. Res. 2010; 4: 727
2e Shinkai H. Onogi S. Tanaka M. Shibata T. Iwao M. Wakitani K. Uchida I. J. Med. Chem. 1998; 41: 1927

3 Záborský O. Šoral M. Fischer R. Tetrahedron Lett. 2015; 56: 2155

4a Malatinský T. Spišáková M. Babjak M. Doháňošová J. Marek J. Moncol J. Fischer R. Eur. J. Org. Chem. 2017; 1086
4b Beňadiková D. Čurillová J. Lacek T. Rakovský E. Moncol J. Doháňošová J. Fischer R. Tetrahedron 2014; 70: 5585
4c Fischer R. Stanko B. Prónayová N. Synlett 2013; 24: 2132

5 Záborský O. Malatinský T. Marek J. Moncol J. Fischer R. Eur. J. Org. Chem. 2016; 3993

6a Katritzky AR. Tala SR. Avan I. J. Org. Chem. 2009; 74: 8690
6b Behr J.-B. Chevrier C. Defoin A. Tarnus C. Streith J. Tetrahedron 2003; 59: 543
6c Stewart AO. Brooks DW. J. Org. Chem. 1992; 57: 5020
6d Johnson JE. Ghafouripour A. Haung YK. Cordes AW. Pennington WT. Exner O. J. Org. Chem. 1985; 50: 993

For selected papers on the asymmetric conjugate additions between N-protected hydroxylamines and enals, see:

7a Dou Q.-Y. Tu Y.-Q. Zhang Y. Tian J.-M. Zhang F.-M. Wang S.-H. Adv. Synth. Catal. 2016; 358: 874
7b Maltsev OV. Kucherenko AS. Chimishkyan AL. Zlotin SG. Tetrahedron: Asymmetry 2010; 21: 2659
7c Juarez-Garcia ME. Yu S. Bode JW. Tetrahedron 2010; 66: 4841
7d Zhao G.-L. Lin S. Korotvička A. Deiana L. Kullberg M. Córdova A. Adv. Synth. Catal. 2010; 352: 2291
7e Ibrahem I. Rios R. Vesely J. Zhao G.-L. Córdova A. Chem. Commun. 2007; 849
7f Ibrahem I. Rios R. Vesely J. Zhao G.-L. Córdova A. Synthesis 2007; 1153

For selected reviews on the proline-catalyzed asymmetric reactions, see:

8a Liu J. Wang L. Synthesis 2017; 49: 960
8b Enders D. Wang C. Liebich JX. Chem. Eur. J. 2009; 15: 11058
8c List B. Tetrahedron 2002; 58: 5573

9a Motorina IA. Sviridova LA. Golubeva GA. Bundel YuG. Chem. Heterocycl. Compd. 1990; 26: 815
9b Motorina IA. Sviridova LA. Golubeva GA. Bundel YuG. Tetrahedron Lett. 1989; 30: 117
9c Zelenin KN. Motorina IA. Sviridova LA. Bezhan IP. Ershov Yu. Golubeva GA. Bundel YuG. Chem. Heterocycl. Compd. 1987; 23: 1018

10 ¹H NMR data for 1-[3-phenylisoxazol-2(3H)-yl]ethanone (4e): ¹H NMR (300 MHz, CDCl₃): δ = 7.39–7.25 (m, 5 H, C₆H₅), 6.69 (dd, J = 3.1, 2.5 Hz, 1 H, 5-H), 6.08 (br s, 1 H, 3-H), 5.25 (dd, J = 3.1, 2.5 Hz, 1 H, 4-H), 2.18 (s, 3 H, CH₃). ¹³C NMR spectrum was not recorded due to the lower quality of the isolated material.

11a Peng B. Geerdink D. Farès C. Maulide N. Angew. Chem. Int. Ed. 2014; 53: 5462
11b Beatty MF. Jennings-White C. Avery MA. J. Chem. Soc., Chem. Commun. 1991; 351

For selected papers on the oxidations of furanose glycals with DMDO, see:

12a Singh I. Seitz O. Org. Lett. 2006; 8: 4319
12b Jung ME. Toyota A. de Clercq E. Balzarini J. Monatsh. Chem. 2002; 133: 499
12c Mann RK. Parsons JG. Rizzacasa MA. J. Chem. Soc., Perkin Trans. 1 1998; 1283
12d Timmers CM. Verheijen JC. van der Marel GA. van Boom JH. Synlett 1997; 851
12e McDonald FE. Gleason MM. J. Am. Chem. Soc. 1996; 118: 6648
12f McVinish LM. Rizzacasa MA. Tetrahedron Lett. 1994; 35: 923
12g Dushin RG. Danishefsky SJ. J. Am. Chem. Soc. 1992; 114: 655
12h Chow K. Danishefsky SJ. J. Org. Chem. 1990; 55: 4211

13 Cheshev P. Marra A. Dondoni A. Carbohydr. Res. 2006; 341: 2714

14a Romeo R. Giofrè SV. Carnovale C. Campisi A. Parenti R. Bandini L. Chiacchio MA. Bioorg. Med. Chem. 2013; 21: 7929
14b Piotrowska DG. Balzarini J. Głowacka IE. Eur. J. Med. Chem. 2012; 47: 501

For selected papers on the acid-catalyzed anomerizations of related methyl furanosides, see:

15a Forsman JJ. Wärnå J. Murzin DYu. Leino R. Eur. J. Org. Chem. 2009; 5666
15b Song Y. Yang R. Ding H. Sun Q. Xiao Q. Ju Y. Synthesis 2011; 1213
15c Li N.-S. Lu J. Piccirilli JA. Org. Lett. 2007; 9: 3009
15d Paquette LA. Zhang Y. J. Org. Chem. 2006; 71: 4353
15e Suzuki T. Chida N. Chem. Lett. 2003; 32: 190
15f Takahashi S. Kuzuhara H. Nakajima M. Tetrahedron 2001; 57: 6915
15g Martin OR. Kurz KG. Rao SP. J. Org. Chem. 1987; 52: 2922

16 Ning J. Kong F. Carbohydr. Res. 2001; 330: 165

17a Prévost M. St-Jean O. Guindon Y. J. Am. Chem. Soc. 2010; 132: 12433
17b Nishida Y. Shingu Y. Dohi H. Kobayashi K. Org. Lett. 2003; 5: 2377
17c Shingu Y. Nishida Y. Dohi H. Kobayashi K. Org. Biomol. Chem. 2003; 1: 2518
17d Gillard JW. Israel M. Tetrahedron Lett. 1981; 22: 513

18a Taber DF. DeMatteo W. Hassan RA. Org. Synth. 2013; 90: 350
18b Hayes CJ. Sherlock AE. Selby MD. Org. Biomol. Chem. 2006; 4: 193

19 CCDC 1558911 (5a), 1558912 (6a), 1558913 (5c), and 1558914 (3e) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.

20a Burla MC. Caliandro R. Carrozzini B. Cascarano GL. Cuocci C. Giacovazzo C. Mallamo M. Mazzone A. Polidori D. J. Appl. Crystallogr. 2015; 48: 306
20b Sheldrick GM. Acta Crystallogr., Sect. A 2015; 71: 3
20c Sheldrick GM. Acta Crystallogr., Sect. C 2015; 71: 3
20d Dolomanov O. Bourhis LJ. Goldea RI. Howard JA. K. Puschmann H. J. Appl. Crystallogr. 2009; 42: 339
20e Palatinus L. Chapuis G. J. Appl. Crystallogr. 2007; 40: 786

21 Parsons S. Flack HD. Wagner T. Acta Crystallogr., Sect. B 2013; 69: 249

Supplementary Material

Supporting Information