Asymmetric synthesis of a chiral secondary grignard reagent

Angewandte Chemie - International Edition

Volumn 39, Issue 17, 2000, Pages 3072-3074

  Hoffmann, Reinhard W ^a   Hölzer, Bettina ^a   Knopff, Oliver ^a   Harms, Klaus ^a  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

Author keywords

Asymmetric synthesis; Grignard reagents; Oxidations

Indexed keywords

ALCOHOL DERIVATIVE; ORGANOMETALLIC COMPOUND; REAGENT;

ARTICLE; CHEMICAL STRUCTURE; ENANTIOMER; OXIDATION; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0039599114     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20000901)39:17<3072::AID-ANIE3072>3.0.CO;2-4     Document Type: Article

References (29)

1. M. Braun, Methoden Org. Chem. (Houben-Weyl) 4th ed. 1952-, Vol. E19d, 1993, pp. 853-1138.
2. a) M. Tanaka, I. Ogata, Bull. Chem. Soc. Jpn. 1975, 48, 1094;
3. b) H. Schumann, B. C. Wassermann, F. E. Hahn, Organometallics 1992, 11, 2803-2811;
4. c) D. Dakternieks, K. Dunn, D. J. Henry, C. H. Schiesser, E. R. Tiekink, Organometallics 1999, 18, 3342-3347.
5. a) F. R. Jensen, K. L. Nakamaye, J. Am. Chem. Soc. 1966, 88, 3437-3438;
6. b) J. San Filippo, J. W. Nicoletti, J. Org. Chem. 1977, 42, 1940-1944.
7. H. M. Walborsky, A. E. Young, J. Am. Chem. Soc. 1964, 86, 3288-3296.
8. a) H. W. H. J. Bodewitz, C. Blomberg, F. Bickelhaupt, Tetrahedron 1973, 29, 719-726;
9. b) H. W. H. J. Bodewitz, C. Blomberg, F. Bickelhaupt, Tetrahedron 1975, 31, 1053-1063.
10. a) J. Villiéras. Bull. Soc. Chim. Fr. 1967, 1511-1520;
11. b) R. C. Hahn, J. Tompkins, Tetrahedron Lett. 1990, 31, 937-940;
12. c) C. DeLima, M. Julia, J.-N. Verpeaux, Synlett 1992, 133-134.
13. R. W. Hoffmann, P. G. Nell, Angew. Chem. 1999, 111, 354-355; Angew. Chem. Int. Ed. 1999, 38, 338-340.
14. R. W. Hoffmann, P. G. Nell, Angew. Chem. 1999, 111, 354-355; Angew. Chem. Int. Ed. 1999, 38, 338-340.
15. R. W. Hoffmann, P. Nell, R. Leo, K. Harms, Chem. Eur. J. 2000, in press.
16. R. W. Hoffmann, O. Knopff, A. Kusche, Angew. Chem. 2000, 112, 1521-1523; Angew. Chem. Int. Ed. 2000, 39, 1462-1464.
17. R. W. Hoffmann, O. Knopff, A. Kusche, Angew. Chem. 2000, 112, 1521-1523; Angew. Chem. Int. Ed. 2000, 39, 1462-1464.
18. The reaction of the sulfoxide 4 to give the Grignard reagent 3 requires at least three equivalents of ethylmagnesium chloride, since the sulfoxide coproduct 6 consumes a further equivalent of ethylmagnesium chloride leading to the formation of diethyl sulfoxide and p-chlorophenylmagnesium chloride. We applied more than three equivalents of ethylmagnesium chloride in order to increase the rate by which 5 is converted into 3, thereby reducing the fraction of 5 which underwent competing racemization.
19. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-143893. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
20. This statement is based on the as yet unproven assumption that addition of the secondary Grignard reagent 3 to phenylisothiocyanate proceeded with retention of configuration.
21. A. G. Davies, B. P. Roberts, J. Chem. Soc. B 1969, 317-321.
22. S. Nazabadioko, R. J. Pèrez, R. Breiva, V. Gotor, Tetrahedron: Asymmetry 1998, 9, 1597-1604.
23. N. J. Lewis, S. Y. Gabhe, M. R. DeLaMater, J. Org. Chem. 1977, 42, 1479-1480.
24. F. A. Davis, J. Wei, A. C. Sheppard, Tetrahedron Lett. 1987, 28, 5115-5118.
25. R. W. Hoffmann, K. Ditrich, Synthesis 1983, 107-109.
26. M. Taddei, A. Ricci, Synthesis 1986, 633-635.
27. a) G. Boche, K. Möbus, K. Harms, M. Marsch, J. Am. Chem. Soc. 1996, 118, 2770-27711;
28. b) M. Husemann, Dissertation, Universität Marburg, 1996.
29. G. Boche, K. Möbus, K. Harms, J. C. W. Lohrenz, M. Marsch, Chem. Eur. J. 1996, 2, 604-607.