Abstract
The copper-catalyzed aziridination of styrene with copper-exchanged zeolite HY (CuHY) and copper(II) triflate (trifluoromethanesulfonate) (Cu(OTf)2) as catalysts is described using N-(p-tolylsulfonyl)imino]phenyliodinane (PhI=NTs) as the nitrene donor. The effects on the ee and yield of the aziridine when the catalyst is modified by the presence of a chiral bis(oxazoline) are investigated in detail. The heterogeneously catalyzed reaction under these conditions shows a slight, but significant, enhancement in ee with increasing conversion at 25 °C. This is not observed in the more rapid homogeneously catalyzed reaction under identical reaction conditions using PhINTs as the nitrene donor. The enhancement in ee is proposed to result from the preferential reaction of the (S)-aziridine with the Cu2+:bis(oxazoline) complex in the presence of PhI=NTs, leading to an enhancement of the (R)-aziridine in the remaining aziridine product.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
R. Noyori, Asymmetric Catalysis in Organic Synthesis (Wiley, New York, 1994).
T. Katsuki and K.B. Sharpless, J. Am. Chem. Soc. 102 (1980) 5974.
W. Zhang, J.L. Loebach, S.R.W. Wilson and E.N. Jacobsen, J. Am. Chem. Soc. 112 (1990) 2801.
J.S. Johnson and D.A. Evans, Acc. Chem. Res. 33 (2000) 325.
K. Soai, T. Shibata and I. Sato, Acc. Chem. Res. 33 (2000) 382.
K. Mikami, M. Terada, T. Korenaga, Y. Matsumoto and S. Matsukawa, Acc. Chem. Res. 33 (2000) 391.
D.G. Blackmond, Acc. Chem. Res. 33 (2000) 402.
G.J. Hutchings, Chem. Commun. (1999) 301.
S. Feast, D. Bethell, P.C.B. Page, F. King, C.H. Rochester, M.R.H. Siddiqui, D.J. Willock and G.J. Hutchings, J. Chem. Soc., Chem. Commun. (1995) 2499.
S. Feast, M.R.H. Siddiqui, R.P.K. Wells, D.J. Willock, F. King, C.H. Rochester, D. Bethell, P.C.B. Page and G.J. Hutchings, J. Catal. 167 (1997) 533.
C. Langham, P. Piaggio, D. Bethell, D.F. Lee, P. McMorn, P.C. Bulman Page, D.J. Willock, C. Sly, F.E. Hancock, F. King and G.J. Hutchings, Chem. Commun. (1998) 1601.
C. Langham, S. Taylor, D. Bethell, P. McMorn, P.C. Bulman Page, D.J. Willock, C. Sly, F.E. Hancock and G.J. Hutchings, J. Chem. Soc., Perkin 2, (1999) 1043.
P. Piaggio, P. McMorn, C. Langham, D. Bethell, P.C. Bulman Page, F.E. Hancock and G.J. Hutchings, New J. Chem. (1998) 1167.
P. Piaggio, C. Langham, P. McMorn, D. Bethell, P.C. Bulman Page, F.E. Hancock, C. Sly and G.J. Hutchings, J. Chem. Soc., Perkin Trans. 2, (2000) 143.
P. Piaggio, P. McMorn, D.M. Murphy, D. Bethell, P.C. Bulman Page, F.E. Hancock, C. Sly, O.J. Kerton and G.J. Hutchings, J. Chem. Soc., Perkin Trans. 2, (2000) 2009.
S. Taylor, J. Gullick, P. McMorn, D. Bethell, P.C. Bulman Page, F.E. Hancock, F. King and G.J. Hutchings, J. Chem. Soc., Perkin Trans. 2, (2001) 1714.
S. Taylor, J. Gullick, P. McMorn, D. Bethell, P.C. Bulman Page, F.E. Hancock, F. King and G.J. Hutchings, J. Chem. Soc., Perkin Trans. 2, (2001) 1724.
E.N. Jacobsen, in Comprehensive Asymmetric Catalysis, Vol. 2, E.N. Jacobsen, A. Pfaltz and H. Yumamoto (eds.) (Springer-Verlag, Berlin, 1999) p. 607.
D.A. Evans, M.M. Faul and M.T.J. Bilodeau, J. Org. Chem. 56 (1991) 6744.
D.A. Evans, M.M. Faul and M.T. Bilodeau, J. Am. Chem. Soc. 116 (1994) 2741.
D.A. Evans, K.A. Woerpel, M.M. Hinman and M.M. Faul, J. Am. Chem. Soc. 113 (1991) 726.
M. Glos and O. Reiser, Org. Lett. 2 (2000) 2045.
M.I. Burguete, J.M. Fraile, J.I. García, E. García-Verdugo, S.V. Luis and J.A. Mayoral, Org. Lett. 2 (2000) 3905.
R.J. Clarke and I.J. Shannon, Chem. Commun. (2001) 1936.
T. Mallat, Z. Bodnar, B. Minder, K. Borszeky and A. Baiker, J. Catal. 168 (1997) 183.
J. Wang, Y. Sun, C. Lebland, R.N. Landua and D.G. Blackmond, J. Catal. 161 (1996) 752.
C. Langham, P. Piaggio, D. Bethell, D.F. Lee, P.C. Bulman Page, D.J. Willock, C. Sly, F.E. Hancock, F. King and G.J. Hutchings, in Catalysis of Organic Reactions, Vol. 3, F.E. Herkes (ed.) (Marcel Dekker, 1998) p. 25.
B.L. Lin, C.R. Clough and G.L. Hillhouse J. Am. Chem. Soc. 124 (2002) 2890.
ADF2002.01 was obtained from SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, http://www.scm.com
C. Fonseca Guerra, J.G. Snijders, G. te Velde and E.J. Baerends, Theor. Chem. Acc. 99 (1998) 391; G. te Velde, F.M. Bickelhaupt, S.J.A. van Gisbergen, C. Fonseca Guerra, E.J. Baerends, J.G. Snijders and T. Ziegler, J. Comput. Chem. 22 (2001) 931.
A.D. Becke, Phys. Rev. A, 38 (1988) 3098.
C. Lee, W. Yang and R.G. Parr, Phys. Rev. B, 37 (1988) 785.
P. Brandt, M.J. Sodergren, P. Gandersson and P.-O. Norrby, J. Am. Chem. Soc. 112 (2000) 8013.
D.A. Evans, S.J. Miller, T. Lectka and P. von Matt, J. Am. Chem. Soc. 121 (1999) 7559.
J. Gullick, S. Taylor, O. Kerton, P. McMorn, F. King, F.E. Hancock, D. Bethell, P.C.B. Page and G.J. Hutchings, Catal. Lett. 75 (2001) 151.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Taylor, S., Gullick, J., Galea, N. et al. Catalytic Asymmetric Heterogeneous Aziridination Using CuHY/bis(oxazoline): Effect of Reaction Conditions on Enantioselectivity. Topics in Catalysis 25, 81–88 (2003). https://doi.org/10.1023/B:TOCA.0000003100.56246.39
Issue Date:
DOI: https://doi.org/10.1023/B:TOCA.0000003100.56246.39