[3+2] Cycloaddition of Oxaziridines with Nitriles: Synthesis of 2,3-Dihydro-1,2,4-Oxadiazoles

Abstract

A new and simpler preparation of 2,3-dihydro-1,2,4 oxadiazoles by synchronous [3+2] cycloaddition between oxaziridines and nitriles is presented.

Key word

cycloaddition - oxaziridines - nitriles - 2,3-dihydro-1,2,4 oxadiazoles - heterocycles

References and Notes

• 1 Bokach NA. Kukushkin VYu. Russ. Chem. Bull.  2006,  55:  1869 
• 2a Azizian J. Madani M. Souzangarzadeh S. Synth. Commun.  2005,  35:  765 
• 2b Szczepankiewicz W. Suwinski J. Karczmarzyk Z. Chem. Heterocycl. Compd.  2004,  40:  801 
• 2c Srivastava RM. Rosa MF. Carvalho CEM. Portugal S. da GM. Brinn IM. Da Canceicao Pereira M. Antunes OAC. Heterocycles  2000,  53:  191 
• 2d Balsamini C. Spadoni G. Bedini A. Tarzia G. Lanfranchi M. Pellinghelli MA. J. Heterocycl. Chem.  1992,  29:  1593 
• 2e Repke DB. Albrecht HP. Moffatt JG. J. Org. Chem.  1975,  40:  2481 
• 3a Singh CP. Hasan H. J. Indian Council Chem.  2002,  19:  46 
• 3b Chimirri A. Grasso S. Montforte A.-M.
  Rao A. Zappala M. Farmaco  1996,  51:  125 
• 3c Mnrao MRG. Karamjit K. Sharma JR. Kalsi PS. Indian J. Heterocycl. Chem.  1995,  5:  151 
• 3d Sterne J. Le Guilcher S. Rousselet M. Therapie  1972,  27:  517 
• 4 Eberson L. McCullough JJ. Hartshorn ChM. Hartshorn MP. J. Chem. Soc., Perkin Trans. 2  1998,  41 
• 5 Yu Y. Watanabe N. Ohno M. Educhi S. J. Chem. Soc., Perkin Trans. 1  1995,  1417 
• 6 Yu Y. Ohno M. Educhi S. J. Chem. Soc., Chem. Commun.  1994,  331 
• 7 Yu Y. Fujita H. Ohno M. Educhi S. Synthesis  1995,  498 
• 8 Plate R. Hermkens PHH. Smits JMM. Nivard RJF. Ottenheijm HCJ. J. Org. Chem.  1987,  52:  1047 
• 9 Wagner G. Chem. Eur. J.  2003,  9:  1503 
• 10 Sustmann R. Tetrahedron Lett.  1971,  2721 
• 11 Kurznetson ML. Kukushkin VYu. J. Org. Chem.  2006,  71:  582 
• 12 Kurznetson ML. Kukushkin VYu. Dement’ev AI. Pombeiro AJL. J. Phys. Chem. A.  2003,  107:  6108 
• 13 Hermkens PHH. Maarseveen JHV. Kruse CG. Scheeren HW. Tetrahedron  1988,  44:  6491 
• 14 Wagner G. Pombeiro AJL. Kukushkin VYu. J. Am. Chem. Soc.  2000,  122:  3106 
• 15 Sarju J. Arbour J. Sayer J. Rohrmoser B. Scherer W. Wagner G. Dalton Trans.  2008,  5302 
• 16 Wagner G. Haukka M. Fraùsto da Silva JJR. Pombeiro AJL. Kukushkin VYu. Inorg. Chem.  2001,  40:  264 
• 17 Fabio M. Ronzini L. Troisi L. Tetrahedron  2008,  64:  4979 
• 19 Fabio M. Ronzini L. Troisi L. Tetrahedron  2007,  63:  12896 
• 22a Osborn HMI. Gemmell N. Harwood LM. J. Chem. Soc., Perkin Trans. 1  2002,  2419 ; and references therein
• 22b Adams JP. Paterson JR. J. Chem. Soc., Perkin Trans. 1  2000,  3695 
• 22c Adams JP. Paterson JR. J. Chem. Soc., Perkin Trans. 1  1999,  749 
• 22d Merino P. Science of Synthesis   Vol. 27:  Thieme; Stuttgart: 2004.  p.511 ; and references therein
• 24 Troisi L. De Lorenzis S. Fabio M. Rosato F. Granito C. Tetrahedron: Asymmetry  2008,  19:  2246 

18

Troisi, L.; Fabio, M.; Rosato, F.; Videtta, V. submitted.

20

Reaction conducted according to general procedure.

21

Reaction conducted using benzonitrile as solvent (10 mL) for 15 h according to the general procedure. Yields, after chromatographic purification, were about 80%.

23

Compound 1: Crude product was purified by flash chromatography on silica gel deactivated with Et₃N (PE-Et₂O, 8:2). ^¹H NMR (400 MHz, CDCl₃): δ = 1.23 (s, 9 H), 6.11 (s, 1 H), 7.25-7.54 (m, 8 H), 7.98 (d, J = 8.1 Hz, 2 H). ^¹³C NMR (100.62 MHz, CDCl₃): δ = 25.0, 60.4, 85.8, 125.3, 126.6, 126.9, 128.0, 128.5, 131.9, 141.6, 161.4. GC-MS (70 eV): m/z = 280 (<1) [M⁺], 177 (50), 121 (35), 105 (20), 77 (25), 57 (100). FTIR (CHCl₃): 3067, 2987, 2927, 2852, 1656, 1494, 1452, 1326 cm^-¹. Anal. Calcd for C₁₈H₂₀N₂O: C, 77.11; H, 7.19; O, 5.71. Found: C, 77.09; H, 7.18; O, 5.69.

25

Diastereomeric ratio determined by ^¹H NMR on the crude product.