Chemoselective Reduction of Functionalized 5-Nitroisoxazoles: Synthesis of 5-Amino- and 5-[Hydroxy(tetrahydrofuran-2-yl)amino]isoxazoles

Abstract

Reduction by using SnCl₂ of easily accessible 5-nitroisoxazoles substituted with an electron-withdrawing group (EWG) has been studied. Whereas the reaction in ethanol yielded 5-aminoisoxazoles, performing the reaction in tetrahydrofuran gave previously unknown 5-[hydroxy(tetrahydrofuran-2-yl)amino]isoxazoles. Both reduction procedures were optimized to afford the corresponding products in good to excellent yields. Some mechanistic details concerning the inclusion of the tetrahydrofuranyl moiety into the reaction product are discussed

Key words

reduction - chemoselectivity - isoxazoles - radical reaction - tetrahydrofuran

• References

• 1a Lang SA, Lin Y.-I In Comprehensive Heterocyclic Chemistry . Vol. 6. Katritzky AR, Rees CW. Pergamon; Oxford: 1984: 1
• 1b Giomi D, Cordero FM, Machetti F In Comprehensive Heterocyclic Chemistry . Vol. 4. Katritzky AR, Ramsden CA, Scriven EF. V, Taylor RJ. K. Elsevier; Oxford: 2008: 365
• 2a Liu T, Dong X, Xue N, Wu R, He Q, Yang B, Hu Y. Bioorg. Med. Chem. 2009; 17: 6279
• 2b Salem AM, Mohamed GM, Sulaiman AM, Mohammed NY. Chem. Pharm. Bull. 2013; 61: 50
• 2c Rowbottom MW, Faraoni R, Chao Q, Campbell BT, Lai AG, Setti E, Ezawa M, Sprankle KG, Abraham S, Tran L, Struss B, Gibney M, Armstrong RC, Gunawardane RN, Nepomuceno RR, Valenta I, Hua H, Gardner MF, Cramer MD, Gitnick D, Insko DE, Apuy JL, Jones-Bolin S, Ghose AK, Herbertz T, Ator MA, Dorsey BD, Ruggeri B, Williams M, Bhagwat S, James J, Holladay MW. J. Med. Chem. 2012; 55: 1082
• 3 Vogl E, Bruns R, Kretschik O, Uhr H, Kaulen J, Kugler M, Wachtler P, Kreiss W, Eberz G. Bioorg. Med. Chem. Lett. 2005; 15: 625
• 4 Hickey ER, Riether D, Ermann M. PCT Int. Appl WO 2012012307, 2012 ; Chem. Abstr. 2012, 156, 203257.
• 5a Kislyi VP, Danilova EB, Semenov VV. Adv. Heterocycl. Chem. 2007; 94: 173
• 5b Hamama WS, Ibrahim ME, Zoorob HH. Synth. Commun. 2013; 43: 2393
• 6a Liu T, Dong X, Xue N, Wu R, He Q, Yang B, Hu Y. Bioorg. Med. Chem. 2000; 17: 6279
• 6b Korany AA. ARKIVOC 2010; (xi): 55
• 6c Polozov AM, Hategan G, Cao H, Kiselyov AS, Zeller W, Singh J. Tetrahedron Lett. 2010; 51: 575
• 6d Nenajdenko VG, Golubinskii IV, Lenkova ON, Shastin AV, Balenkova ES. Russ. Chem. Bull. 2005; 54: 1728
• 6e Mounir AA. M. Synth. Commun. 2011; 41: 331
• 7a Yu GJ, Yang B, Verkman AS, Kurth MJ. Synlett 2010; 1063
• 7b Ji Z, Ahmed AA, Albert DH, Bouska JJ, Bousquet PF, Cunha GA, Glaser KB, Guo J, Li J, Marcotte PA, Moskey MD, Pease LJ, Stewart KD, Yates M, Davidsena SK, Michaelides MR. Bioorg. Med. Chem. Lett. 2006; 16: 4326
• 7c Laufer SA, Margutti S, Fritz MD. ChemMedChem 2006; 1: 197
• 8a Volkova YA, Averina EB, Grishin YK, Bruheim P, Kuznetsova TS, Zefirov NS. J. Org. Chem. 2010; 75: 3047
• 8b Averina EB, Volkova YA, Samoilichenko YV, Grishin YK, Rybakov VB, Kutateladze AG, Elyashberg ME, Kuznetsova TS, Zefirov NS. Tetrahedron Lett. 2012; 53: 1472 ; The regiochemistry reported in ref. 8a was revised in ref. 8b
• 9 The X-ray crystal structures of 2b have been assigned the number CCDC-820549 and described in our previous manuscript, see ref. 8b.
• 10a Matthews DP, McCarthy JR. J. Org. Chem. 1990; 55: 2973
• 10b Chen J, Zhang Y.-F, Zheng X, Vij A, Wingate D, Meng D, White K, Kirchmeier RL, Shreeve JM. Inorg. Chem. 1996; 35: 1590
• 10c Bravo A, Bjørsvik H.-R, Fontana F, Liguori L, Minisci F. J. Org. Chem. 1997; 62: 3849
• 10d Hirano K, Sakaguchi S, Ishii Y. Tetrahedron Lett. 2002; 43: 3617
• 11 Shiosaki M, Unno M, Hanamoto T. J. Org. Chem. 2010; 75: 8326
• 12a Akindele T, Yamada K, Tomioka K. Acc. Chem. Res. 2009; 42: 345
• 12b Ishida A, Sugita D, Itoh Y, Takamuku S. J. Am. Chem. Soc. 1995; 117: 11687
• 12c Alves MJ, Gilchrist TL, Sousa JH. J. Chem. Soc., Perkin Trans. 1 1999; 1305
• 13a Xiang J, Fuchs PL. J. Am. Chem. Soc. 1996; 118: 11986
• 13b Clark AJ, Rooke S, Sparey TJ, Taylor PC. Tetrahedron Lett. 1996; 37: 909
• 13c Xiang J, Jiang W, Gong J, Fuchs PL. J. Am. Chem. Soc. 1997; 119: 4123
• 13d Xiang J, Evarts J, Rivkin A, Curran DP, Fuchs PL. Tetrahedron Lett. 1998; 39: 4163
• 14a Gong J, Fuchs PL. J. Am. Chem. Soc. 1996; 118: 4486
• 14b Xiang J, Jiang W, Fuchs PL. Tetrahedron Lett. 1997; 38: 6635
• 14c Yang Y, Huang H, Zhang X, Zeng W, Liang Y. Synthesis 2013; 45: 3137
• 15a Fontand F, Minis F, Yan YM, Zhao L. Tetrahedron Lett. 1993; 34: 2517
• 15b Inoue A, Shinokubo H, Oshima K. Synlett 1999; 1582
• 16 Matsuo Y, Zhang Y, Nakamura E. Org. Lett. 2008; 10: 1251
• 17 Kim S, Kim N, Chung W, Cho CH. Synlett 2001; 937
• 18 Guo S, Yuan Y, Xiang J. Org. Lett. 2013; 15: 4654
• 19 Jung JC, Choi HC, Kim YH. Tetrahedron Lett. 1993; 34: 3581
• 20 Yamamoto Y, Maekawa M, Akindele T, Yamada K, Tomioka K. Tetrahedron 2005; 61: 379
• 21a Marradi M, Corsi M, Cicchi S, Bonanni M, Cardona F, Goti A. Heterocycles 2009; 79: 883
• 21b Argyropoulos NG, Gkizis P, Coutouli-Argyropoulou E. Tetrahedron 2008; 64: 8752
• 21c Bonanni M, Marradi M, Cicchi S, Goti A. Synlett 2008; 197
• 21d Dondoni A, Perrone D. Tetrahedron 2003; 59: 4261
• 21e Dondoni A, Giovannini PP, Perrone D. J. Org. Chem. 2002; 67: 7203
• 22a Zhang X.-M, Tu Y.-Q, Zhang F.-M, Shao H, Meng X. Angew. Chem. Int. Ed. 2011; 50: 3916
• 22b Thorson JS, Goff RD. US 20120094946, 2012 ; Chem. Abstr. 2012, 156, 552114.
• 22c Goff RD, Thorson JS. J. Med. Chem. 2010; 53: 8129
• 22d Lantos I, Flisak J, Liu L, Matsuoka R, Mendelson W, Stevenson D, Tubman K, Tucker L, Zhang W.-Y, Adams J, Sorenson M, Garigipati R, Erhardt K, Ross S. J. Org. Chem. 1997; 62: 5385
• 23 Crystallographic data for compound 3m (CCDC-865299) can be obtained free of charge from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: [phone]; E-mail: [e-mail]; Web site: www.ccdc.cam.ac.uk/conts/retrieving.html.