Highly enantiomerically enriched ketone homoenolate reagents prepared by (-)-sparteine-mediated γ-deprotonation of achiral 1-alkenyl carbamates

Angewandte Chemie - International Edition

Volumn 43, Issue 11, 2004, Pages 1423-1427

  Seppi, Michael ^a   Kalkofen, Rainer ^a   Reupohl, Jens ^a   Fröhlich, Roland ^a   Hoppe, Dieter ^a  

^a UNIVERSITY OF MÜNSTER   (Germany)

Author keywords

Asymmetric synthesis; Homoaldol reaction; Lithium; Sparteine; Titanium

Indexed keywords

CARBON; LITHIUM COMPOUNDS; REACTION KINETICS; STEREOCHEMISTRY;

DEPROTONATION; DIASTEREOSELECTIVITY; REAGENTS;

KETONES;

CARBAMIC ACID DERIVATIVE; KETONE; LITHIUM DERIVATIVE; SPARTEINE;

ARTICLE; ENANTIOMER; PROTON TRANSPORT; STEREOCHEMISTRY;

EID: 4544265506     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200352966     Document Type: Article

References (47)

1. Reviews: a) D. Hoppe, T. Hense, Angew. Chem. 1997, 109, 2376; Angew. Chem. Int. Ed. Engl. 1997, 36, 2282;
2. Reviews: a) D. Hoppe, T. Hense, Angew. Chem. 1997, 109, 2376; Angew. Chem. Int. Ed. Engl. 1997, 36, 2282;
3. b) D. Hoppe, F. Marr, M. Brüggemann, Top. Organomet. Chem. 2003, 5, 61;
4. c) P. Beak, T. A. Johnson, D. D. Kim, S. H. Lim, Top. Organomet. Chem. 2003, 5, 134;
5. d) H. Ahlbrecht, U. Beyer, Synthesis 1999, 365.
6. a) T. Krämer, J.-R. Schwark, D. Hoppe, Tetrahedron Lett. 1989, 30, 7037;
7. b) D. Hoppe, O. Zschage, Angew. Chem. 1989, 101, 67; Angew. Chem. Int. Ed. Engl. 1989, 28, 69;
8. b) D. Hoppe, O. Zschage, Angew. Chem. 1989, 101, 67; Angew. Chem. Int. Ed. Engl. 1989, 28, 69;
9. c) D. Hoppe, O. Zschage, Tetrahedron 1992, 48, 5657;
10. d) T. Krämer, D. Hoppe, Tetrahedron Lett. 1987, 28, 5149;
11. e) M. C. Whisler, L. V. Vaillancourt, P. Beak, Org. Lett. 2000, 2, 2655.
12. The direction of chirality transfer is reversed if 1 reacts from the 1-exo-conformation rather than the 1-endo configuration (as shown in Scheme 1).
13. D. Hoppe, T. Krämer, Angew. Chem. 1986, 98, 171; Angew. Chem. Int. Ed. Engl. 1986, 25, 160.
14. D. Hoppe, T. Krämer, Angew. Chem. 1986, 98, 171; Angew. Chem. Int. Ed. Engl. 1986, 25, 160.
15. At least half of the racemic starting material is lost during this process.
16. O. Zschage, J.-R. Schwark, D. Hoppe, Angew. Chem. 1990, 102, 336; Angew. Chem. Int. Ed. Engl. 1990, 29, 296.
17. O. Zschage, J.-R. Schwark, D. Hoppe, Angew. Chem. 1990, 102, 336; Angew. Chem. Int. Ed. Engl. 1990, 29, 296.
18. M. Özlügedik, J. Kristensen, B. Wibbeling, R. Fröhlich, D. Hoppe, Eur. J. Org. Chem. 2002, 414.
19. a) H. Roder, G. Helmchen, E.-M. Peters, K. Peters, H.-G. von Schnering, Angew. Chem. 1984, 96, 895; Angew. Chem. Int. Ed. Engl. 1984, 23, 898;
20. a) H. Roder, G. Helmchen, E.-M. Peters, K. Peters, H.-G. von Schnering, Angew. Chem. 1984, 96, 895; Angew. Chem. Int. Ed. Engl. 1984, 23, 898;
21. b) D. Heimbach, D. Hoppe, Synlett 2000, 950;
22. c) M. Reggelin, C. Zurr, Synthesis 2000, 1.
23. For the asymmetric γ-deprotonation of enamines see the ref. [1d] and, in particular, the contributions of the author cited therein.
24. J. G. Peters, M. Seppi, R. Fröhlich, D. Hoppe, Synthesis 2002, 381.
25. M. Seppi, Dissertation, Universität Münster, 2001.
26. -3, Flack parameter -0.030(18), hydrogens calculated and refined as riding atoms. Data sets were collected with an Enraf-Nonius CAD4 and Nonius KappaCCD diffractometers. Programs used: data collection EXPRESS (Nonius B.V., 1994) and COLLECT (Nonius B.V., 1998), data reduction MolEN (K. Fair, Enraf-Nonius B.V., 1990) and Denzo-SMN (Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307), absorption corrections for CCD data SORTAV (R. H. Blessing, Acta Crystallogr. Sect. A 1995, 51, 33; R. H. Blessing, J. Appl. Crystallogr. 1997, 30, 421), structure solution SHELXS-97 (G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467), structure refinement SHELXL-97 (G. M. Sheldrick, Universität Göttingen, 1997, E. Keller, Graphik SCHAKAL, Universität Freiburg, 1997). CCDC-219962 and CCDC-219961 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ ccdc.cam.ac.uk).
27. -3, Flack parameter -0.030(18), hydrogens calculated and refined as riding atoms. Data sets were collected with an Enraf-Nonius CAD4 and Nonius KappaCCD diffractometers. Programs used: data collection EXPRESS (Nonius B.V., 1994) and COLLECT (Nonius B.V., 1998), data reduction MolEN (K. Fair, Enraf-Nonius B.V., 1990) and Denzo-SMN (Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307), absorption corrections for CCD data SORTAV (R. H. Blessing, Acta Crystallogr. Sect. A 1995, 51, 33; R. H. Blessing, J. Appl. Crystallogr. 1997, 30, 421), structure solution SHELXS-97 (G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467), structure refinement SHELXL-97 (G. M. Sheldrick, Universität Göttingen, 1997, E. Keller, Graphik SCHAKAL, Universität Freiburg, 1997). CCDC-219962 and CCDC-219961 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ ccdc.cam.ac.uk).
28. -3, Flack parameter -0.030(18), hydrogens calculated and refined as riding atoms. Data sets were collected with an Enraf-Nonius CAD4 and Nonius KappaCCD diffractometers. Programs used: data collection EXPRESS (Nonius B.V., 1994) and COLLECT (Nonius B.V., 1998), data reduction MolEN (K. Fair, Enraf-Nonius B.V., 1990) and Denzo-SMN (Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307), absorption corrections for CCD data SORTAV (R. H. Blessing, Acta Crystallogr. Sect. A 1995, 51, 33; R. H. Blessing, J. Appl. Crystallogr. 1997, 30, 421), structure solution SHELXS-97 (G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467), structure refinement SHELXL-97 (G. M. Sheldrick, Universität Göttingen, 1997, E. Keller, Graphik SCHAKAL, Universität Freiburg, 1997). CCDC-219962 and CCDC-219961 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ ccdc.cam.ac.uk).
29. -3, Flack parameter -0.030(18), hydrogens calculated and refined as riding atoms. Data sets were collected with an Enraf-Nonius CAD4 and Nonius KappaCCD diffractometers. Programs used: data collection EXPRESS (Nonius B.V., 1994) and COLLECT (Nonius B.V., 1998), data reduction MolEN (K. Fair, Enraf-Nonius B.V., 1990) and Denzo-SMN (Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307), absorption corrections for CCD data SORTAV (R. H. Blessing, Acta Crystallogr. Sect. A 1995, 51, 33; R. H. Blessing, J. Appl. Crystallogr. 1997, 30, 421), structure solution SHELXS-97 (G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467), structure refinement SHELXL-97 (G. M. Sheldrick, Universität Göttingen, 1997, E. Keller, Graphik SCHAKAL, Universität Freiburg, 1997). CCDC-219962 and CCDC-219961 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ ccdc.cam.ac.uk).
30. -3, Flack parameter -0.030(18), hydrogens calculated and refined as riding atoms. Data sets were collected with an Enraf-Nonius CAD4 and Nonius KappaCCD diffractometers. Programs used: data collection EXPRESS (Nonius B.V., 1994) and COLLECT (Nonius B.V., 1998), data reduction MolEN (K. Fair, Enraf-Nonius B.V., 1990) and Denzo-SMN (Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307), absorption corrections for CCD data SORTAV (R. H. Blessing, Acta Crystallogr. Sect. A 1995, 51, 33; R. H. Blessing, J. Appl. Crystallogr. 1997, 30, 421), structure solution SHELXS-97 (G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467), structure refinement SHELXL-97 (G. M. Sheldrick, Universität Göttingen, 1997, E. Keller, Graphik SCHAKAL, Universität Freiburg, 1997). CCDC-219962 and CCDC-219961 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ ccdc.cam.ac.uk).
31. -3, Flack parameter -0.030(18), hydrogens calculated and refined as riding atoms. Data sets were collected with an Enraf-Nonius CAD4 and Nonius KappaCCD diffractometers. Programs used: data collection EXPRESS (Nonius B.V., 1994) and COLLECT (Nonius B.V., 1998), data reduction MolEN (K. Fair, Enraf-Nonius B.V., 1990) and Denzo-SMN (Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307), absorption corrections for CCD data SORTAV (R. H. Blessing, Acta Crystallogr. Sect. A 1995, 51, 33; R. H. Blessing, J. Appl. Crystallogr. 1997, 30, 421), structure solution SHELXS-97 (G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467), structure refinement SHELXL-97 (G. M. Sheldrick, Universität Göttingen, 1997, E. Keller, Graphik SCHAKAL, Universität Freiburg, 1997). CCDC-219962 and CCDC-219961 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ ccdc.cam.ac.uk).
32. H. Paulsen, C. Graeve, D. Hoppe, Synthesis 1996, 141.
33. a) A. Carstens, D. Hoppe, Tetrahedron 1994, 50, 6697;
34. b) C. Derwing, D. Hoppe, Synthesis 1996, 149;
35. c) C. Derwing, H. Frank, D. Hoppe, Eur. J. Org. Chem. 1999, 3511;
36. d) F. Hammerschmidt, A. Hanninger, P. Perric, H. Völlenkle, H. Werner, Eur. J. Org. Chem. 1999, 3511;
37. e) N. C. Faibish, Y. S. Park, S. Lee, P. Beak, J. Am. Chem. Soc. 1997, 119, 11561.
38. Reviews on titanation: a) M. T. Reetz, Organotitanium Reagents in Organic Synthesis, Springer, Berlin, 1986;
39. b) B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 32;
40. b) B. Weidmann, D. Seebach, Angew. Chem. 1983, 95, 12; Angew. Chem. Int. Ed. Engl. 1983, 22, 32;
41. c) "Organotitanium Chemistry": M. T. Reetz in Organometallics in Synthesis (Ed.: M. Schlosser), Wiley, Chichester, 2002, p. 817.
42. E' additions of aldehydes have been reported.[1]
43. The decreased enantioselectivity of 86% ee for the addition of the lithium compound 6a to 2,2-dimethylpropanal (71, Table 1, entry 9) indicates a tendency for anti addition. The tendency increases for branched alkanals and n-alkanals and causes the predominant formation of addition products ent-8.
44. a) V. E. Williams, R. P. Lemieux, G. R. J. Thatcher, J. Org. Chem. 1996, 61, 1927;
45. b) R. J. Wehmschulte, P. P. Power, J. Am. Chem. Soc. 1997, 119, 2847.
46. H. E. Zimmerman, M. D. Traxler, J. Am. Chem. Soc. 1957, 79, 1920.
47. J. Reubner, R. Fröhlich, D. Hoppe, Org. Lett. 2004, 6, in press.