Aziridination of Alkenes
FULL PAPER
2-[(2RS,3SR)-2,3-Diphenylaziridin-1-yl]isoindoline-1,3-dione:
Yield:
[1] Aziridines and Epoxides in Organic Synthesis (Ed.: A. K. Yudin),
Wiley-VCH, Weinheim, 2006.
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[8] For examples see: a) T. Saito, M. Sakairi, A. Abika, Tetrahedron
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Angew. Chem. Int. Ed. 2001, 40, 1433–1436.
79% from cis-stilbene, N-aminophthalimide (3) and (diacetoxyiodo)ben-
zene (19). Spectroscopic data were consistent with that previously report-
ed.[40]
2-(2,2-Diphenylaziridin-1-yl)isoindoline-1,3-dione: Yield: 75% from 1,1-
diphenylethene, N-aminophthalimide (3) and (diacetoxyiodo)benzene
(19). Spectroscopic were data consistent with that previously reported.[41]
2-(2-Phenylaziridin-1-yl)isoindoline-1,3-dione (37): Yield: 78% from sty-
rene, N-aminophthalimide (3) and (diacetoxyiodo)benzene (19). Spectro-
scopic data were consistent with that previously reported.[11]
2-Methyl-3-(2-phenylaziridin-1-yl)quinazolin-4(3H)one (42): Yield: 84%
from styrene, 2-amino-3-methylquinazolin-1-one (26) and (diacetoxyio-
do)benzene (19). Spectroscopic data were consistent with that previously
reported.[11]
3-[2-(4-Bromophenyl)aziridin-1-yl]-2-methylquinazolin-4(3H)one
(29)
(R1 =Q, R2 =4-BrC6H4): Yield: 65% (waxy solid) from 4-bromostyrene,
2-amino-3-methylquinazolin-1-one (26) and (diacetoxyiodo)benzene (19).
IR (film): n˜ =2924, 1675, 1598, 1472, 1328, 908, 731 cmÀ1 1H NMR
;
(400 MHz, CDCl3): d=8.17 (1H, dd, J=8.0 1.3Hz), 7.64 (1H, td, J=7.0,
1.3Hz), 7.60 (1H, d, J=7.0 Hz), 7.54 (2H, d, J=8.0 Hz), 7.46 (1H, td,
J=6.6, 1.8 Hz), 7.39 (2H, d, J=8.0 Hz), 3.58 (1H, dd, J=8.0, 5.6 Hz),
3.00 (1H, dd, J=8.0, 2.4 Hz), 2.82 (1H, dd, J=5.6, 2.3Hz), 2.60 ppm
(3H, s); 13C NMR (126 MHz, CDCl3): d=160.0, 153.8, 146.0, 135.5, 134.0,
131.8, 131.6, 128.3, 126.5, 126.3, 122.2, 121.4, 47.2, 43.8, 22.0 ppm; LRMS
(ESIÀH+): m/z (%): 359.0 (18) 358.0 (97), 357.0 (18), 356.0 (100)
[M+H]+; HRMS: calcd for C17H1579BrN3O+: 356.0393; found: 356.0395
[M+H]+.
[9] J. Li, J.-L. Liang, P. W. H. Chan, C.-M. Che, Tetrahedron Lett. 2004,
45, 2685–2688.
[10] D. W. Jones, J. Chem. Soc. Perkin Trans. 1 1972, 225–228.
[11] D. J. Anderson, T. L. Gilchrist, D. C. Howell, C. W. Rees, J. Chem.
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[12] R. S. Atkinson, J. R. Malpass, J. Chem. Soc. Perkin Trans. 1 1977,
2242–2249.
Methyl 1-(1,3-dioxoisoindolin-2-yl)aziridine-2-carboxylate (38): Yield:
65% from methyl acrylate, N-aminophthalimide (3) and (diacetoxyiodo)-
benzene (19). Spectroscopic data were consistent with those previously
reported.[11]
[13] J. Li, P. W. H. Chan, C.-M. Che, Org. Lett. 2005, 7, 5801–5804.
[14] T. Siu, A. K. Yudin, J. Am. Chem. Soc. 2002, 124, 530–531.
[15] a) E. Hatzigrigoriou, A. Varvoglis, M. Bakola-Christianopoulou, J.
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Chem. Soc. 1990, 112, 5672–5673; c) T. Kitamura, C. H. Lee, Y. Ta-
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[16] a) For a review see R. D. Richardson, T. Wirth, Angew. Chem. 2006,
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Dohi, Y. Kita, Kagaku 2006, 61, 68–69.
[17] For the first example of an enantioselective oxidation catalysed by
enantiopure iodoarenes see: R. D. Richardson, T. K. Page, S. Alter-
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[18] A. Bravo, F. Fontana, G. Fronza, F. Minisci, A. Serri, Tetrahedron
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Methyl 1-(2-methyl-4-oxoquinazolin-3(4H)yl)aziridine-2-carboxylate (29)
(R1 =Q, R2 =CO2Me): Yield: 58% from methyl acrylate, 2-amino-3-
methylquinazolin-1-one (26) and (diacetoxyiodo)benzene (19). Spectro-
scopic data were consistent with those previously reported.[11]
2-[2-(3-Nitrophenyl)aziridin-1-yl]isoindoline-1,3-dione (29) (R1 =Phthal,
R2 =3-(NO2)C6H4): Yield: 71% from 3-nitrostyrene, N-aminophthalimide
(3) and (diacetoxyiodo)benzene (19). IR (nujol mull): n˜ =1783, 1720,
1529, 1346, 1159, 881, 703 cmÀ1 1H NMR (500 MHz, CDCl3) d=8.24
;
(1H, t, J=1.8 Hz), 8.13(1H, dt, J=7.9, 1.3Hz), 7.77–7.33(3H, m), 7.68–
7.64 (2H, m), 7.50 (1H, t, J=8.0 Hz), 3.61 (1H, dd, J=8.0, 6.5 Hz), 2.93
(1H, dd, J=8.0, 2.5 Hz), 2.74 (1H, dd, J=6.5, 2.5 Hz) 2.71 ppm (3H, s);
13C NMR (126 MHz, CDCl3) d=164.9, 138.8, 135.1, 134.3, 133.4, 130.2,
129.6, 124.5, 123.3 ppm; HRMS: calcd for C16H12N3O4+: 310.0822; found:
310.0825 [M+H]+. Compound previously reported[42] but no NMR data
were found.
2-Methyl-3-[2-(3-nitrophenyl)aziridin-1-yl]quinazolin-4(3H)one
(29)
(R1 =Q, R2 =3-NO2C6H4): Yield: 43% from 3-nitrostyrene, 2-amino-3-
methylquinazolin-1-one (26), and (diacetoxyiodo)benzene (19) as an
amorphous solid. IR (nujol mull): n˜ =1676, 1595, 1531, 1344, 884,
700 cmÀ1 1H NMR (500 MHz, CDCl3): d=8.24 (1H, t, J=1.9 Hz), 8.14
;
(2H, td, J=6.9, 1.8 Hz), 7.81 (1H, d, J=7.6 Hz), 7.66 (1H, td, J=6.9,
1.3Hz), 7.55 (1H, d, J=8.1 Hz), 7.54 (1H, t, J=8.0 Hz), 7.39 (1H, t, J=
7.1 Hz), 3.89 (1H, dd, J=8.0, 5.5 Hz), 3.01 (1H, dd, J=8.0, 2.0 Hz), 2.84
(1H, dd, J=5.5, 2.1 Hz) 2.71 ppm (3H, s); 13C NMR (126 MHz, CDCl3):
d=158.7, 152.6, 147.6, 137.8, 133.2, 132.1, 128.7, 125.6, 125.3, 122.1, 120.7,
120.3, 45.2, 42.8, 21.5 ppm; HRMS: calcd for C17H15N4O3+: 323.1139;
found: 323.1141 [M+H]+.
[19] a) D. W. Jones, J. Chem. Soc. Chem. Commun. 1972, 884; b) L.
Heosch, A. S. Dreiding, Chimia 1969, 23, 405–408; c) T. Fuchigami,
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[20] G. F. Koser, Top. Curr. Chem. 2000, 208, 137–183.
[21] Mixing alkenes with (diacetoxyiodo)benzene in dichloromethane at
room temperature does not result in the 1,2-diacetoxyalkane. This is
in contrast to the reaction when other ligands are used on the
iodane (see reference [20])
Acknowledgements
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1998, 583–589.
[23] M. Schmeisser, K. Dahmen, P. Sartori, Chem. Ber. 1967, 100, 1633–
1637.
We thank the EPSRC for funding and the UniversitØ de Rennes, Rennes
(France) for a visiting studentship (to M.D.).
[24] M. Ochiai in Chemistry of Hypervalent Compounds (Ed.: K.
Akiba), Wiley-VCH, New York, 1999, pp. 359–387.
Chem. Eur. J. 2007, 13, 6745 – 6754
ꢁ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6753