Iron-Catalyzed Aziridination Reactions
FULL PAPERS
254 nm); ret. time=18 min (S) [minor] and 20 min (R)
[major] (40% ee).[4b,24]
Int. Ed. Engl. 1994, 33, 599; b) J. B. Sweeney, Chem.
Soc. Rev. 2002, 31, 247; c) W. McCoull, F. A. Davies,
Synthesis 2000, 1347; d) P. Duban, R. H. Dodd, Synlett
2003, 1571; e) P. Müller, C. Fruit, Chem. Rev. 2003, 103,
2905; f) C. Moessner, C. Bolm, in: Transition Metals
For Organic Chemistry: Building Blocks and Fine
Chemicals, 2nd edn., (Eds.: M. Beller, C. Bolm), Vol.
II, Wiley/VCH, Weinheim, 2004, p 389; g) Aziridines
and Epoxides in Organic Synthesis, (Ed.: A. K. Yudin),
Wiley-VCH, Weinheim, 2006, p 1.
Representative Procedure for the Conversion of
Olefins [use of TsNH2 (6b)]
Iodobenzene diacetate (161 mg, 0.5 mmol) was added to the
solution of TsNH2 (6b, 43 mg, 0.25 mmol), MgO (50 mg,
1.25 mmol) and MS 4 powder (400 mg) in acetonitrile
(2 mL). After the addition of styrene (4a, 520 mg, 0.57 mL,
5 mmol, 20 equiv.) and Fe(OTf)2 (8.8 mg, 0.025 mmol), the
R
[2] For overviews focusing on aziridine transformations,
see: a) I. D. G. Watson, L. Yu, A. K. Yudin, Acc. Chem.
Res. 2006, 39, 194; b) B. Zwanenburg, P. ten Holte, Top.
Curr. Chem. 2001, 216, 93; c) W. McCoull, F. A. Davis,
Synthesis 2000, 1347.
[3] a) S. Lociuro, L. Pellacani, P. A. Tardella, Tetrahedron
Lett. 1983, 24, 593; b) S. Fioravanti, M. A. Loreto, L.
Pellacani, P. A. Tardella, J. Org. Chem. 1985, 50, 5365;
c) D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Am.
Chem. Soc. 1994, 116, 2742; for the synthesis of a-N-to-
sylamido ketones by oxidative ring opening of aziri-
dines, see: d) K. Surendra, N. S. Krishnaveni, K. R.
Rao, Tetrahedron Lett. 2005, 46, 4111; e) M. S. Reddy,
M. Narender, K. R. Rao, Tetrahedron Lett. 2005, 46,
1299.
[4] For Cu-catalyzed aziridinations, see: a) D. A. Evans,
M. A. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56,
6744; b) D. A. Evans, M. A. Faul, M. T. Bilodeau, B. A.
Andersson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115,
5328; c) Z. Li, K. R. Conser, E. N. Jacobsen, J. Am.
Chem. Soc. 1993, 115, 5326; d) M. J. Sçdergren, D. A.
Alonso, P. G. Anderson, Tetrahedron: Asymmetry 1997,
8, 3563; e) P. Dauban, R. H. Dodd, J. Org. Chem. 1999,
64, 5304; f) D. B. Llewellyn, D. Adamson, B. A. Arndt-
sen, Org. Lett. 2000, 2, 4165; g) W. Adam, K. J. Rosch-
mann, C. R. Saha-Mçller, Eur. J. Org. Chem. 2000, 557;
h) P. Dauban, L. Sanire, L. Tarrade, R. H. Dodd, J.
Am. Chem. Soc. 2001, 123, 7707; i) M. Shi, C.-J. Wang,
A. S. C. Chan, Tetrahedron: Asymmetry 2001, 12, 3105;
j) S. L. Jain, B. Sain, Tetrahedron Lett. 2003, 44, 575;
k) P. Comba, M. Merz, H. Pritzkow, Eur. J. Inorg.
Chem. 2003, 1711; l) H. L. Kwong, D. Liu, K.-Y. Chan,
C.-S. Lee, K.-H. Hung, C.-M. Che, Tetrahedron Lett.
2004, 45, 3965; m) H. Han, I, Bae, E. J. Yoo, J. Lee, Y.
Do, S. Chang, Org. Lett. 2004, 6, 4109; n) T. C. H. Lam,
W.-L. Mak, W.-L. Wong, H.-L. Kwong, H. H. Y. Sung,
S. M. F. Lo, I. D. Williams, W.-H. Leung, Organometal-
lics 2004, 23, 1247; o) S. L. Jain, V. B. Sharma, B. Sain,
Synth. Commun. 2005, 35, 9; p) S. L. Jain, B. Sain, J.
Mol. Catal. A 2003, 195, 283; q) P. Dauban, R. H.
Dodd, Org. Lett. 2000, 2, 2327; r) D. Leca, A. Tous-
saint, C. Mereau, L. Fensterbank, E. Lacôte, M. Ma-
larcria, Org. Lett. 2004, 6, 3573; s) K. M. Gillespie, E. J.
Crust, R. J. Deeth, P. Scott, Chem. Commun. 2001, 785.
[5] For Rh-catalyzed aziridinations, see: a) G. F. Keaney,
J. L. Wood, Tetrahedron Lett. 2005, 46, 4031; b) A. J.
Catino, J. M. Nichols, R. E. Forslund, M. P. Doyle, Org.
Lett. 2005, 7, 2787; c) K. Guthikonda, J. Du Bois, J.
Am. Chem. Soc. 2002, 124, 13672; d) P. Müller, C.
Baud, Y. Jacquier, Tetrahedron Lett. 1996, 37, 1543;
e) I. Nägeli, C. Baud, G. Bernardinelli, Y. Jacquier, M.
Moran, P Müller, Helv. Chim. Acta 1997, 80, 1087.
reaction mixture was stirred under argon for 24 h. The mix-
ture was the filtrated and the solvent evaporated (rotary
evaporator). The remaining mixture was separated by
column chromatography (silica gel; ethyl acetate:pentane=
1:5 as eluent) affording aziridine 5a as a white solid; yield:
41 mg (60%).
4-Methyl-N-(2-oxononyl)benzenesulfonamide (3d): mp
104–1078C; 1H NMR(400 MHz, CDCl 3): d=0.71 (t, J=
6.6 Hz, 3H), 0.90–1.13 (m, 8H), 1.31–1.38 (m, 2H), 2.16 (t,
J=7.4 Hz, 2H), 2.26 (s, 3H), 3.66 (d, J=4.7 Hz, 2H), 5.16
(broad t, J=4.7 Hz, 1H), 7.14 (d, J=8.5 Hz, 2H), 7.57 (d,
J=8.5 Hz, 2H); 13C NMR(75 MHz, CDCl 3): d=203.8,
143.8, 136.0, 129.8, 127.2, 51.3, 40.1, 31.5, 28.9, 23.6, 22.6,
21.5, 14.0; MS (EI, 70 eV): m/z (%)=309 (MÀ2H)+; IR
(KBr): n=3273, 2931, 2856, 1722, 1321, 1160, 691 cmÀ1; anal.
calcd. for C16H25NO3S (311.44): C 61.70, H 8.09, N 4.50;
found: C 61.94, H 8.19, N 4.44.
Preparation of PhINSO2[2-(5-methyl)pyridinyl] (2d)
E
KOH (1.18 g, 21 mmol) was added to a solution of 5-
methyl-2-pyridinesulfonamide (1.72 g, 10 mmol) in methanol
(30 mL). Then iodobenzene diacetate (3.22 g, 10 mmol) was
added at 08C. The reaction mixture was allowed to warm to
room temperature and was stirred for 45 min. The reaction
mixture was partially concentrated under reduced pressure
and the white solid was filtered. The crystals were washed
with distilled water affording PhINSO2[2-(5-methyl)pyridin-
U
yl] (2d) as a white solid; yield: 2.2 g (61%); mp 1448C (det-
onates); 1H NMR(400 MHz, DMSO- d6): d=2.28 (s, 3H),
7.39–7.45 (m, 2H), 7.48–7.54 (m, 1H), 7.59–7.62 (m, 1H),
7.65–7.70 (m, 1H), 7.87–7.90 (m, 2H), 8.31–8.32 (m, 1H);
13C NMR(75 MHz, DMSO- d6): d=159.6, 149.0, 138.7,
135.4, 133.1, 131.2, 131.0, 119.4, 119.3, 18.3; IR(KBr): n=
1567, 1465, 1444, 1271, 1132, 1099, 922, 898, 825, 736, 673,
629 cmÀ1; anal. calcd. for C12H11IN2O2S (357.49): C 38.52, H
2.96, N 7.49; found: C 38.42, H 3.18, N 7.43.
Acknowledgements
We are grateful to the Fonds der Chemischen Industrie and to
the Deutsche Forschungsgemeinschaft (DFG) within the SPP
1118 for continuous support of our research program.
References
[1] For reviews on aziridination reactions, see: a) D.
Tanner, Angew. Chem. 1994, 106, 625; Angew. Chem.
Adv. Synth. Catal. 2008, 350, 1835 – 1840
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