Synthesis of Stable 1H-Azirines Reinvestigated: A Structural Corrigendum

Abstract

The isoquinoline-catalyzed synthesis of pretended 1H-azirines from phenacyl bromides and N,N′-dialkylcarbodiimides was repeated. The products do not possess the structure of antiaromatic 1H-azirines, but simple N-acyl-N,N′-dialkylureas were formed instead. This structural corrigendum was confirmed by the independent synthesis of the known ureas and comparison of their ¹H NMR and ¹³C NMR spectroscopic data in the case of six compounds. Thus, 1H-azirines keep their classification as very short-lived intermediates.

Key words

acylation - antiaromatic heterocycles - structure - assignment by spectroscopy - ureas

• References and Notes


For reviews on 1H-azirines and 2H-azirines, see:
• 1a Backes J In Houben-Weyl . Vol. E16c nd; Klamann D. Thieme; Stuttgart: 1992: 321
• 1b Nair V In The Chemistry of Heterocyclic Compounds, Small-Ring Heterocycles. Vol. 42, Part 1. Hassner A. Wiley; New York: 1983: 215
• 1c Pearson WH, Lian BW, Bergmeier SC In Comprehensive Heterocyclic Chemistry II . Vol. 1A. Padwa A. Pergamon; New York: 1996: 1
• 1d Palacios F, Ochoa de Retana AN, Martinez de Marigorta E, de Los Santos JM. Eur. J. Org. Chem. 2001; 2401
• 1e Gilchrist TL. Aldrichimica Acta 2001; 34: 51
• 1f Rai KM. L, Hassner A In Advances in Strained and Interesting Organic Molecules . Vol. 8. Halton B. Jai Press; Greenwich: 2000: 187
• 1g Fowler FW. Adv. Heterocycl. Chem. 1971; 13: 45
• 1h Wentrup C. Adv. Heterocycl. Chem. 1981; 28: 231
• 2a Miller TW, Tristram EW, Wolf FJ. J. Antibiot. 1971; 24: 48
• 2b Molinski TF, Ireland CM. J. Org. Chem. 1988; 53: 2103
• 2c Salomon CE, Williams DH, Faulkner DJ. J. Nat. Prod. 1995; 58: 1463
• 2d Stapley EO, Hendlin D, Jackson M, Miller AK, Hernandez S, Mata JM. J. Antibiot. 1971; 24: 42
• 2e Davis FA, Reddy GV, Liu H. J. Am. Chem. Soc. 1995; 117: 3651
• 2f Davis FA, Liu H, Liang C.-H, Reddy GV, Zhang Y, Fang T, Titus DD. J. Org. Chem. 1999; 64: 8929
• 3 Regitz M, Arnold B, Danion D, Schubert H, Fusser G. Bull. Soc. Chim. Belg. 1981; 90: 615
• 4a Jacox ME, Milligan DE. J. Am. Chem. Soc. 1963; 85: 278
• 4b Kodama S. J. Phys. Chem. 1988; 92: 5019
• 5 Maier G, Schmidt C, Reisenauer HP, Endlein E, Becker D, Eckwert J, Hess BA, Schaad LJ. Chem. Ber. 1993; 126: 2337
• 6a Fowler FW, Hassner A. J. Am. Chem. Soc. 1968; 90: 2875
• 6b Anderson DJ, Gilchrist TL, Rees CW. Chem. Commun. 1969; 147
• 6c Gilchrist TL, Gymer GE, Rees CW. Chem. Commun. 1971; 1519
• 6d Anderson DJ, Gilchrist TL, Gymer GE, Rees CW. J. Chem. Soc., Perkin Trans. 1 1973; 550
• 6e Gilchrist TL, Gymer GE, Rees CW. J. Chem. Soc., Perkin Trans. 1 1973; 555
• 6f Atkinson RS, Grimshire MJ. J. Chem. Soc., Perkin Trans. 1 1986; 1215
• 7 Gilchrist TL, Gymer GE, Rees CW. J. Chem. Soc., Perkin Trans. 1 1975; 1
• 8a Mitchell G, Rees CW. J. Chem. Soc., Chem. Commun. 1986; 399
• 8b Mitchell G, Rees CW. J. Chem. Soc., Perkin Trans. 1 1987; 413
• 9a Huisgen R, Blaschke H. Chem. Ber. 1965; 98: 2985
• 9b Meinwald J, Aue DH. J. Am. Chem. Soc. 1966; 88: 2849
• 10 Gilchrist TL, Gymer GE, Rees CW. J. Chem. Soc., Chem. Commun. 1973; 835
• 11 Gilchrist TL, Rees CW, Thomas C. J. Chem. Soc., Perkin Trans. 1 1975; 8
• 12a Wentrup C, Crow WD. Tetrahedron 1970; 26: 3965
• 12b Thétaz C, Wentrup C. J. Am. Chem. Soc. 1976; 98: 1258
• 13 Wentrup C. Helv. Chim. Acta 1972; 55: 1613
• 14a Clark DT. Theoret. Chim. Acta (Berl.) 1969; 15: 225
• 14b Hopkinson AC, Lien MH, Yates K, Csizmadia IG. Int. J. Quantum Chem. 1977; 12: 355
• 14c Bock H, Dammel R. Chem. Ber. 1987; 120: 1971
• 14d Alcami M, Mó O, Yáñez M. J. Am. Chem. Soc. 1993; 115: 11074
• 14e Lathan WA, Radom L, Hariharan PC, Hehre WJ, Pople JA. Top. Curr. Chem. 1973; 40: 1
• 15a Mó O, Yáñez M, Elguero J. J. Mol. Struct. (Theochem) 1989; 201: 17
• 15b Byun Y.-G, Saebo S, Pittman CU. J. Am. Chem. Soc. 1991; 113: 3689
• 15c Malar EJ. P. Tetrahedron 1996; 52: 4709
• 16a Budzelaar PH. M, Cremer D, Wallasch M, Würthwein E.-U, Schleyer P.v.R. J. Am. Chem. Soc. 1987; 109: 6290
• 16b Alcami M, de Paz JL. G, Yáñez M. J. Comp. Chem. 1989; 10: 468
• 17a Würthwein E.-U. J. Org. Chem. 1984; 49: 2971
• 17b Mó O, de Paz JL. G, Yáñez M. J. Phys. Chem. 1987; 91: 6484
• 18 Čársky P, Hess BA, Schaad LJ. J. Am. Chem. Soc. 1983; 105: 396
• 19 Alizadeh A, Rezvanian A. Synlett 2012; 23: 859
• 20 For the complete characterization of 8a–f, see the Supporting Information.
• 21a Lessene G, Smith BJ, Gable RW, Baell JB. J. Org. Chem. 2009; 74: 6511
• 21b Corriu RJ. P, Lanneau GF, Perrot-Petta M. Synthesis 1991; 954
• 21c Neves Filho RA. W, de Oliveira RN, Srivastava RM. J. Braz. Chem. Soc. 2007; 18: 1410
• 21d Quintanilla MG, Montero G, Hierro AG, Diaz JM, Bassani S. Acta Chem. Scand. 1999; 53: 928
• 21e Kishikawa K, Eida H, Kohmoto S, Yamamoto M, Yamada K. Synthesis 1994; 173
• 22a Bamberger E. Ber. Dtsch. Chem. Ges. 1887; 20: 3338
• 22b Schmidt E, van Ark HH. Arch. Pharm. 1900; 238: 321
• 22c Babcock SH, Nakamura FI, Fuson RC. J. Am. Chem. Soc. 1932; 54: 4407
• 22d Krollpfeiffer F, Müller A. Ber. Dtsch. Chem. Ges. B 1933; 66: 739
• 22e Babcock SH, Fuson RC. J. Am. Chem. Soc. 1933; 55: 2946
• 23a Kröhnke F, Heffe W. Ber. Dtsch. Chem. Ges. B 1937; 70: 864
• 23b Pearson RG, Dillon RL. J. Am. Chem. Soc. 1948; 70: 1933
• 23c Pearson RG, Sandy AC. J. Am. Chem. Soc. 1951; 73: 931
• 24a King LC. J. Am. Chem. Soc. 1944; 66: 894
• 24b King LC. J. Am. Chem. Soc. 1944; 66: 1612
• 24c King LC, McWhirter M, Rowland RL. J. Am. Chem. Soc. 1948; 70: 239
• 24d Huffman JW, Zengin G, Wu M.-J, Lu J, Hynd G, Bushell K, Thompson AL. S, Bushell S, Tartal C, Hurst DP, Reggio PH, Selley DE, Cassidy MP, Wiley JL, Martin BR. Bioorg. Med. Chem. 2005; 13: 89
• 24e Brusotti G, Habermann J, Azzolina O, Collina S. Lett. Org. Chem. 2006; 3: 943
• 25 Kröhnke F. Ber. Dtsch. Chem. Ges. B 1933; 66: 604
• 26 Ślebioda M. Tetrahedron 1995; 51: 7829