Syntheses and 15N NMR Spectra of Iminodiaziridines
3923–3927; c) F. H. A. Rummens, R. H. Krystynak, J. Am.
Chem. Soc. 1972, 94, 6914–6921.
of this work. We express our gratitude to Mrs. Elfriede Ruckdeschel
and Dr. Matthias Grüne, University of Würzburg, for taking high-
field NMR spectra of products of iminodiaziridines. We thank the
Deutsche Forschungsgemeinschaft and the Fonds der Chemischen
Industrie, Frankfurt am Main, for financial support.
[15]
[16]
a) S. I. Burmistrov, Yu. V. Sukhoruchkin, Zh. Obshch. Khim.
1963, 33, 1227–1233; b) I. A. Larionova, A. V. Golounin, V. A.
Sokolenko, Russ. J. Org. Chem. 2006, 42, 766–767.
Ring-opening isomerizations of three-membered rings with
exocyclic double bonds have been observed; a) aziridinones: I.
Lengyel, J. C. Sheehan, Angew. Chem. 1968, 80, 27–37; Angew.
Chem. Int. Ed. Engl. 1968, 7, 25–36; b) iminoaziridines: H.
Quast, P. Schäfer, Tetrahedron Lett. 1977, 18, 1057–1060; c)
protonated iminoaziridines: H. Quast, S. Aldenkortt, B. Freud-
enreich, P. Schäfer, E.-M. Peters, K. Peters, H. G. von Schner-
ing, E.-U. Würthwein, Liebigs Ann. 1996, 87–98.
a) C. J. M. Stirling, Chem. Rev. 1978, 78, 517–567; b) S.
Hughes, G. Griffiths, C. J. M. Stirling, J. Chem. Soc. Perkin
Trans. 2 1987, 1253–1264; c) C. W. Spangler, Chem. Rev. 1976,
76, 187–217.
For the thermolysis of diaziridinones via a nitrenoid fragment,
see: P. E. McGann, J. T. Groves, F. D. Greene, G. M. Stack,
R. J. Majeste, L. M. Trefonas, J. Org. Chem. 1978, 43, 922–925.
k3bǞ3c + 2k3cǞ3b = (5.9Ϯ0.1)ϫ10–5 s–1, 3b/3c 96.8:3.2 at
35.5 °C. In contrast, at a temperature of 40 °C, the valence
isomerization 2a/8e required ca. 3 months to reach the equilib-
rium; 2k2aǞ8e + k8eǞ2a = (1.335Ϯ0.005)ϫ10–5 s–1, 2a/8e
90.7:9.3 at 60.0 °C; ref.[7c]
a) U. Schuchardt, L. A. Ortellado, G. Zelada, J. Chem. Res.
(S) 1983, 270–271; b) H. Quast, T. Hergenröther, Chem. Ber.
1992, 125, 2095–2101; c) R. V. Hoffman, Z. Zhao, A. Costales,
D. Clarke, J. Org. Chem. 2002, 67, 5284–5294; d) A. Gómez-
Zavaglia, I. D. Reva, L. Frija, M. L. Cristiano, R. Fausto, J.
Photochem. Photobiol. A: Chem. 2006, 179, 243–255; e)
L. M. T. Frija, I. D. Reva, A. Gómez-Zavaglia, M. L. S. Cristi-
ano, R. Fausto, Photochem. Photobiol. Sci. 2007, 6, 1170–1176.
a) R. F. Meyer, J. Org. Chem. 1965, 30, 3451–3454; b) S. Sarel,
J. T. Klug, A. Taube, J. Org. Chem. 1970, 35, 1850–1857; c) K.
Ramakrishnan, J. B. Fulton, J. Warkentin, Tetrahedron 1976,
32, 2685–2688; d) P. Legrel, M. Baudy-Floc’h, A. Robert, Tet-
rahedron Lett. 1986, 27, 5609–5610; e) J. B. Fulton, J. Warken-
tin, Can. J. Chem. 1987, 65, 1177–1184; f) H. Quast, T. Herg-
enröther, Chem. Ber. 1992, 125, 2625–2627.
a) H. G. Aurich, H.-G. Scharpenberg, Chem. Ber. 1973, 106,
1881–1896; b) T. Sasaki, S. Eguchi, T. Ogawa, Heterocycles
1975, 3, 193–196.
K. Peters, H. G. von Schnering, Chem. Ber. 1976, 109, 1384–
1388.
K. Peters, E.-M. Peters, G. Philipp, H. Quast, Z. Kristallogr.
NCS 2000, 215, 305–306.
3aH-Benzimidazoles have previously been postulated as elusive
intermediates: a) C. W. Rees, Pure Appl. Chem. 1979, 51, 1243–
1253; b) C. A. Ramsden, H. L. Rose, J. Chem. Soc. Perkin
Trans. 1 1995, 615–617.
R. Trave, L. Garanti, G. Zecchi, J. Chem. Soc. Perkin Trans. 1
1987, 1533–1536.
T. L. Gilchrist, M. E. Peek, C. W. Rees, J. Chem. Soc., Chem.
Commun. 1975, 914–915.
Restricted rotation of tert-butyl groups at low temperatures has
often been documented: S. Sternhell, “Rotation About Single
Bonds in Organic Molecules”, in Dynamic Nuclear Magnetic
Resonance Spectroscopy (Eds.: L. M. Jackman, F. A. Cotton),
1st ed., Academic Press, New York, 1975, chapter 6, pp. 163–
201.
These results are in accord with scrambling of labeled substitu-
ents in the photodenitrogenation products of phenyl-substi-
tuted 5-imino-4,5-dihydro-1H-tetrazoles: H. Quast, A. Fuß, U.
Nahr, Chem. Ber. 1985, 118, 2164–2185.
[1] Reviews: a) G. L’abbé, Angew. Chem. 1980, 92, 277–290; An-
gew. Chem. Int. Ed. Engl. 1980, 19, 276–289; b) G. L’abbé, in
Lectures in Heterocyclic Chemistry, vol. 9 (Eds.: R. N. Castle,
R. Neidlein), J. Heterocycl. Chem. 1987, 24 (Suppl.), pp. S-51–
S-58; c) T. H. Chan, B. S. Ong, Tetrahedron 1980, 36, 2269–
2289; d) J. A. Deyrup, in The Chemistry of Ethers, Crown
Ethers, Hydroxyl Groups and Their Sulphur Analogues (Ed.: S.
Patai), Wiley, Chichester, UK, 1980, part 1, pp. 177–214; e)
P. J. Stang, in The Chemistry of Ethers, Crown Ethers, Hydroxyl
Groups and Their Sulphur Analogues (Ed.: S. Patai), Wiley,
Chichester, UK, 1980, part 2, pp. 859–879; f) H. W. Heine, in
The Chemistry of Heterocyclic Compounds, vol. 42 (Small Ring
Heterocycles) (Ed.: A. Hassner), Wiley, Chichester, UK, 1983,
part 2, pp. 616–628; g) R. V. Hoffman, V. Cesare, in Science of
Synthesis, vol. 21 (Ed.: S. M. Weinreb), Thieme, Stuttgart,
2005, pp. 591–608.
[2] a) H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem.
2001, 113, 2056–2075; Angew. Chem. Int. Ed. 2001, 40, 2004–
2021; b) V. D. Bock, H. Hiemstra, J. H. van Maarseveen, Eur. J.
Org. Chem. 2006, 51–68; c) M. V. Gil, M. J. Arévalo, Ó. López,
Synthesis 2007, 1589–1620; d) H. Nandivada, X. Jiang, J. Lah-
ann, Adv. Mater. 2007, 19, 2197–2208; e) W. H. Binder, C.
Kluger, Curr. Org. Chem. 2006, 10, 1791–1815.
[3] a) M. Shipman, Synlett 2006, 3205–3217; b) E. J. Corey, K.
Ritter, M. Yus, C. Najera, Tetrahedron Lett. 1987, 28, 3547–
3550; c) J. K. Crandall, E. Rambo, Tetrahedron 2002, 58, 7027–
7036.
[4] S. K. Richardson, A. R. Howell, Synthesis 2007, 2755–2778.
[5] H. Quast, S. Aldenkortt, B. Freudenreich, P. Schäfer, M. Hage-
dorn, J. Lehmann, K. Banert, J. Org. Chem. 2007, 72, 1659–
1666.
[6] a) H. Quast, E. Spiegel, Angew. Chem. 1977, 89, 112–113; An-
gew. Chem. Int. Ed. Engl. 1977, 16, 109–110; b) H. Quast, K.-
H. Ross, E. Spiegel, K. Peters, H. G. von Schnering, Angew.
Chem. 1977, 89, 202–203; Angew. Chem. Int. Ed. Engl. 1977,
16, 177–178; c) B. Zhao, H. Du, Y. Shi, Org. Lett. 2008, 10,
1087–1090.
[7] a) H. Quast, E. Schmitt, Angew. Chem. 1969, 81, 429–430; An-
gew. Chem. Int. Ed. Engl. 1969, 8, 449–450; b) H. Quast, E.
Schmitt, Angew. Chem. 1969, 81, 428; Angew. Chem. Int. Ed.
Engl. 1969, 8, 448; c) H. Quast, E. Schmitt, Chem. Ber. 1970,
103, 1234–1249; d) C. J. Wilkerson, F. D. Greene, J. Org. Chem.
1975, 40, 3112–3118; e) G. L’abbé, A. Verbruggen, T. Minami,
S. Toppet, J. Org. Chem. 1981, 46, 4478–4481.
[8] a) R. Ohme, H. Preuschhof, Justus Liebigs Ann. Chem. 1969,
721, 25–33; b) A. Heesing, G. Imsieke, G. Maleck, R.
Peppmöller, H. Schulze, Chem. Ber. 1970, 103, 539–552.
[9] H. Quast, L. W. Bieber, J. Org. Chem. 2008, 73, 3738–3744.
[10] a) F. Kurzer, K. Douraghi-Zadeh, Chem. Rev. 1967, 67, 107–
152; b) H. Ulrich, Chemistry and Technology of Carbodiimides,
1st ed., Wiley-VCH, Weinheim, 2007.
[11] a) P. Molina, E. Aller, A. Lorenzo, Synlett 2003, 714–716; b)
W.-X. Zhang, Z. Hou, Org. Biomol. Chem. 2008, 6, 1720–1730.
[12] a) O. Westphal, W. de Burlet, Angew. Chem. 1945, 58, 77; b)
P. A. S. Smith, H. R. Alul, R. L. Baumgarten, J. Am. Chem.
Soc. 1964, 86, 1139–1145; c) E. Schmitz, R. Ohme, D. Muraw-
ski, Chem. Ber. 1965, 98, 2516–2524.
[13] a) P. von Rague Schleyer, R. D. Nicholas, J. Am. Chem. Soc.
1961, 83, 182–187; b) J. E. Bertie, M. G. Norton, Can. J. Chem.
1970, 48, 3889–3902; c) R. W. Mitchell, J. A. Merritt, Spectro-
chim. Acta A 1971, 27, 1609–1618.
[14] a) G. J. Karabatsos, S. S. Lande, Tetrahedron 1968, 24, 3907–
3922; b) G. J. Karabatsos, R. A. Taller, Tetrahedron 1968, 24,
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
J. C. Gilbert, J. R. Butler, J. Am. Chem. Soc. 1970, 92, 2168–
2169.
For the similar ring-expansion of 2,2-diphenyl-N-tosylimino-
thiirane, see ref.[1b]
Eur. J. Org. Chem. 2009, 3940–3952
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3951