LETTER
Aminosulfoximines in Copper Catalyses
783
(3) (a) Mock, W. L.; Tsay, J.-T. J. Am. Chem. Soc. 1989, 111,
4467. (b) Mock, W. L.; Zhang, J. Z. J. Biol. Chem. 1991,
266, 6393. (c) Bolm, C.; Kahmann, J. D.; Moll, G.
Tetrahedron Lett. 1997, 38, 1169. (d) Bolm, C.; Moll, G.;
Kahmann, J. D. Chem. Eur. J. 2001, 7, 1118. (e) Bolm, C.;
Müller, D.; Hackenberger, C. P. R. Org. Lett. 2002, 4, 893.
(f) Bolm, C.; Müller, D.; Dalhoff, C.; Hackenberger, C. P.
R.; Weinhold, E. Bioorg. Med. Chem. Lett. 2003, 13, 3207.
(4) For selected contibutions, see: (a) Reggelin, M.; Heinrich,
T. Angew. Chem. Int. Ed. 1998, 37, 2883; Angew. Chem.
1998, 110, 3005. (b) Harmata, M.; Hong, X.; Barnes, C. L.
Tetrahedron Lett. 2003, 44, 7261. (c) Koep, S.; Gais, H.-J.;
Raabe, G. J. Am. Chem. Soc. 2003, 125, 13243.
yield and ee could be improved to 44% and 88%, respec-
tively, by increasing the amount of olefin and ligand to 20
equivalents and 30 mol%, respectively (entry 2). Finally,
use of aminosulfoximine 1g yielded 9c with even 91% ee.
In this case, however, 50 mol% of the catalyst were
applied and the product yield was only 53% (Table 2,
entry 3).
Table 2 Asymmetric Copper-Catalyzed Reaction between Methyl
Puryvate (7a) and a-Methylstyrene (10)a
(5) Reviews: (a) Harmata, M. Chemtracts 2003, 16, 660.
(b) Okamura, H.; Bolm, C. Chem. Lett. 2004, 33, 482.
(6) Bolm, C.; Müller, J.; Schlingloff, G.; Zehnder, M.;
Neuburger, M. J. Chem. Soc., Chem. Commun. 1993, 182.
(7) Bolm, C.; Müller, P. Acta Chem. Scand. 1996, 50, 305.
(8) For further applications, see: (a) Bolm, C.; Felder, M.;
Müller, J. Synlett 1992, 439. (b) Bolm, C.; Felder, M.
Tetrahedron Lett. 1993, 34, 6041. (c) Bolm, C.; Seger, A.;
Felder, M. Tetrahedron Lett. 1993, 34, 8079. (d) Bolm, C.;
Felder, M. Synlett 1994, 655.
(9) For Cu-catalyzed cycloaddition reactions, see: (a)Bolm, C.;
Simic, O. J. Am. Chem. Soc. 2001, 123, 3830. (b) Bolm, C.;
Martin, M.; Simic, O.; Verrucci, M. Org. Lett. 2003, 5, 427.
(10) For Pd-catalyzed allylic alkylations, see: (a) Bolm, C.;
Simic, O.; Martin, M. Synlett 2001, 12, 1878. (b) Harmata,
M.; Ghosh, S. K. Org. Lett. 2001, 3, 3321.
Entry 10 (Equiv) Sulfoximine (amount)
Yield of 9c ee of 9c
(%)
(%)b
1
2
3
10
20
20
(S)-1a (10 mol%)
(S)-1a (30 mol%)
(S)-1g (50 mol%)
11
86
44
88
53
91
a Reaction conditions: 7a (0.5 mmol), olefin 10, Cu(ClO4)2 (prepared
in situ from CuCl2 and 2 AgClO4), sulfoximine 1a or 1g, CH2Cl2 (2
mL), r.t., 48 h.
(11) Bolm, C.; Verrucci, M.; Simic, O.; Cozzi, P. G.; Raabe, G.;
Okamura, H. Chem. Commun. 2003, 2826.
(12) Langner, M.; Bolm, C. Angew. Chem. Int. Ed. 2004, 43,
5984; Angew. Chem. 2004, 116, 6110.
b Determined by HPLC using a chiral column (Chiralcel OB-H). The
absolute configuration of 9c was assigned in analogy to 9a.
(13) For the Pd-catalyzed coupling, see: (a) Bolm, C.;
Hildebrand, J. P. Tetrahedron Lett. 1998, 39, 5731.
(b) Bolm, C.; Hildebrand, J. P. J. Org. Chem. 2000, 65, 169.
(c) Bolm, C.; Hildebrand, J. P.; Rudolph, J. Synthesis 2000,
911.
(14) For the Cu-mediated coupling, see: Cho, G. Y.; Remy, P.;
Jansson, J.; Moessner, C.; Bolm, C. Org. Lett. 2004, 6, 3293.
(15) For examples of highly enantioselective carbonyl-ene
reaction of olefins to ethyl glyoxalate or methyl pyruvate,
see: (a) Maruoka, K.; Hoshino, Y.; Shirasaki, T.;
In conclusion, the application of aminosulfoximines as
ligands in Cu-catalyzed carbonyl-ene reactions was de-
monstrated. The resulting hydroxy esters 9 have been ob-
tained with high enantiomeric excesses (up to 91% ee) in
moderate yields. Those enantioselectivities reach up to the
values achieved with Evans’ well-established Cu(II)-t-
Bu-box catalyst system.15d Current studies are directed to-
wards an expansion of the substrate scope combined with
further process optimizations with the goal of achieving
higher product yields.
Yamamoto, H. Tetrahedron Lett. 1988, 29, 3967.
(b) Mikami, K.; Terada, M.; Nakai, T. J. Am. Chem. Soc.
1990, 112, 3949. (c) Mikami, K. Pure Appl. Chem. 1996,
68, 639. (d) Evans, D. A.; Tregay, S. W.; Burgey, C. S.;
Paras, N. A.; Vojkovsky, T. J. Am. Chem. Soc. 2000, 122,
7936. (e) Yuan, Y.; Zhang, X.; Ding, K. Angew. Chem. Int.
Ed. 2003, 42, 5478; Angew. Chem. 2003, 115, 5636.
(f) Guo, H.; Wang, X.; Ding, K. Tetrahedron Lett. 2004, 45,
2009. (g) Reviews: Mikami, K.; Shimizu, M. Chem. Rev.
1992, 92, 1021. (h) See also: Mikami, K.; Terada, M. In
Comprehensive Asymmetric Catalysis, Vol. III; Jacobsen, E.
N.; Pfaltz, A.; Yamamoto, H., Eds.; Springer: Berlin, 1999,
1143. (i) Dias, L. C. Curr. Org. Chem. 2000, 4, 305.
(16) Coppola, G. M.; Schuster, H. F. a-Hydroxy Acids in
Enantioselective Syntheses; VCH: Weinheim, 1997.
(17) Bolm, C.; Martin, M.; Gescheidt, G.; Palivan, C.;
Neshchadin, D.; Bertagnolli, H.; Feth, M. P.; Schweiger, A.;
Mitrikas, G.; Harmer, J. J. Am. Chem. Soc. 2003, 125, 6222.
(18) A pronounced effect of ortho-alkoxy groups was observed in
hetero-Diels–Alder reactions catalyzed by copper
Acknowledgment
We are grateful to the Fonds der Chemischen Industrie and to the
Deutsche Forschungsgemeinschaft (DFG) within the SFB 380
‘Asymmetric Synthesis by Chemical and Biological Methods’ for
financial support. Mr. M. Reichelt is acknowledged for experimen-
tal contributions.
References
(1) Review: (a) Johnson, C. R. Acc. Chem. Res. 1973, 6, 341.
(b) Pyne, S. G. Sulfur Rep. 1992, 12, 57. (c) Reggelin, M.;
Zur, C. Synthesis 2000, 1.
(2) Selected reviews: (a) Meister, A. Biochem. Biophys. Acta
1995, 35. (b) Anderson, M. E. Chem.-Biol. Interact. 1998,
111, 1. (c) Muldoon, L. L.; Walker-Rosenfeld, L. S. L.;
Hale, C.; Purcell, S. E.; Bennett, L. C.; Neuwelt, E. A. J.
Pharmacol. Exp. Ther. 2001, 296, 797.
complexes bearing N-quinolyl sulfoximines. For details, see
ref. 11.
Synlett 2005, No. 5, 781–784 © Thieme Stuttgart · New York