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Synthesis 2013; 45(11): 1524-1528
DOI: 10.1055/s-0033-1338436
DOI: 10.1055/s-0033-1338436
paper
Synthesis of Furoxans from Styrenes under Basic or Neutral Conditions
Further Information
Publication History
Received: 05 March 2013
Accepted after revision: 29 March 2013
Publication Date:
14 May 2013 (online)
Abstract
Furoxans (1,2,5-oxadiazole 2-oxides) can be synthesized from the corresponding styrenes using NOBF4 under basic or even almost neutral reaction conditions. Acid-sensitive functional groups are tolerated under the developed basic conditions. For the substrates having poor reactivity, almost neutral conditions (using pyridine equimolar to NOBF4) are suitable for better yields.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
- Supporting Information
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References
- 1a Sheremetev AB, Makhova NN, Friedrichsen W. Adv. Heterocycl. Chem. 2001; 78: 65
- 1b Gasco A, Boulton AJ. Adv. Heterocycl. Chem. 1981; 29: 251
- 2a Fruttero R, Crosetti M, Chegaev K, Guglielmo S, Gasco A, Berardi F, Niso M, Perrone R, Panaro MA, Colabufo NA. J. Med. Chem. 2010; 53: 5467
- 2b Rai G, Sayed AA, Lea WA, Luecke HF, Chakrapani H, Prast-Nielsen S, Jadhav A, Leister W, Shen M, Inglese J, Austin CP, Keefer L, Arnér ES. J, Simeonov A, Maloney DJ, Williams DL, Thomas CJ. J. Med. Chem. 2009; 52: 6474
- 2c Cena C, Bertinaria M, Boschi D, Giorgis M, Gasco A. ARKIVOC 2006; (vii): 301
- 2d Grosso ED, Boschi D, Lazzarato L, Cena C, Stilo AD, Fruttero R, Moro S, Gasco A. Chem. Biodiversity 2005; 2: 886
- 2e Medana C, Ermondi G, Fruttero R, Stilo AD, Ferretti C, Gasco A. J. Med. Chem. 1994; 37: 4412
- 2f Calvino R, Fruttero R, Ghigo D, Bosia A, Pescarmona GP, Gasco A. J. Med. Chem. 1992; 35: 3296
- 2g Feelisch M, Schönafinger K, Noack E. Biochem. Pharmacol. 1992; 44: 1149
- 2h Ghigo D, Heller R, Calvino R, Alessio P, Fruttero R, Gasco A, Bosia A, Pescarmona G. Biochem. Pharmacol. 1992; 43: 1281
- 3a Cena C, Lolli ML, Lazzarato L, Guaita E, Morini G, Coruzzi G, McElroy SP, Megson IL, Fruttero R, Gasco A. J. Med. Chem. 2003; 46: 747
- 3b Fruttero R, Boschi D, Stilo AD, Gasco A. J. Med. Chem. 1995; 38: 4944
- 4a Curini M, Epifano F, Marcotullio MC, Rosati O, Ballini R, Bosica G. Tetrahedron Lett. 2000; 41: 8817
- 4b Klamann D, Koser W, Weyerstahl P, Fligge M. Chem. Ber. 1965; 98: 1831
- 5 Wiley RH, Wakefield BJ. J. Org. Chem. 1960; 25: 546
- 6 Alimenti G, Grifantini M, Gualteri F, Stein ML. Tetrahedron 1968; 24: 395
- 7a Dinh NH, Ly NT, Hoan PV. J. Heterocycl. Chem. 2006; 43: 1657
- 7b Gasco AM, Fruttero R, Sorba G, Gasco A. Liebigs Ann. Chem. 1991; 1211
- 7c Fruttero R, Ferrarotti B, Serafino A, Stilo AD, Gasco A. J. Heterocycl. Chem. 1989; 26: 1345
- 8 Aliphatic internal alkenes such as oct-4-ene and cyclohexene were tried as substrates in this furoxan synthesis transformation, but the desired furoxans were obtained in much lower yield (<10%) than in the cases using styrene derivatives as substrates.
- 9 Velázquez C, Rao PN. P, McDonald R, Knaus EE. Bioorg. Med. Chem. 2005; 13: 2749
- 10 The reaction of NOBF4 and pyridine has been reported, see: Olah GA, Olah JA, Overchuk NA. J. Org. Chem. 1965; 30: 3373
- 11 CCDC 922872 (2a) and CCDC 922871 (2l) contain supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax +44(1223)336033; E-mail: deposit@ccdc.cam.ac.uk.
- 12a Mallory FB, Cammarata A. J. Am. Chem. Soc. 1966; 88: 61
- 12b Freeman JP. J. Org. Chem. 1963; 28: 2508
- 13 The structures of the minor regioisomers were assigned by NMR spectroscopy and GC-MS analysis.
- 14 The proposed reaction mechanism is as follows: Electrophilic addition of a nitrosyl cation to an alkene, followed by deprotonation by pyridine, affords a nitrosoalkene. A second addition of a nitrosyl cation to the nitrosoalkene and cyclization leads to a furoxan.
- 15 Mitchell WR, Paton RM. ARKIVOC 2009; (xiv): 200