Parallel kinetic resolution of racemic aldehydes by use of asymmetric Horner-Wadsworth-Emmons reactions

Organic Letters

Volumn 2, Issue 4, 2000, Pages 535-538

  Pedersen, Torben M ^a   Jensen, Jakob F ^a   Humble, Rikke E ^a   Rein, Tobias ^a   Tanner, David ^a   Bodmann, Kerstin ^b   Reiser, Oliver ^b  

^a TECHNICAL UNIVERSITY OF DENMARK   (Denmark)

^b UNIVERSITY OF REGENSBURG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000017001     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol991387h     Document Type: Article

References (31)

1. For a review, see: Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249.
2. Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1997, 119, 2584.
3. For a review, see: (a) Rein, T.; Reiser, O. Acta Chem. Scand. 1996, 50, 369. Selected recent examples:
4. (b) Abiko, A.; Masamune, S. Tetrahedron Lett. 1996, 37, 1077.
5. (c) Kumamoto, T.; Koga, K. Chem. Pharm. Bull. 1997, 45, 753.
6. (d) Dai, W.-M.; Wu, J.; Huang, X. Tetrahedron: Asymmetry 1997, 8, 1979.
7. (e) Mizuno, M.; Fujii, K.; Tomioka, K. Angew. Chem. 1998, 110, 525; Angew. Chem., Int. Ed. Engl. 1998, 37, 515.
8. (e) Mizuno, M.; Fujii, K.; Tomioka, K. Angew. Chem. 1998, 110, 525; Angew. Chem., Int. Ed. Engl. 1998, 37, 515.
9. (f) Vaulont, I.; Gais, H.-J.; Reuter, N.; Schmitz, E.; Ossenkamp, R. K. L. Eur. J. Org. Chem. 1998, 805.
10. (g) Tullis, J. S.; Vares, L.; Kann, N.; Norrby, P.-O.; Rein, T. J. Org. Chem. 1998, 63, 8284.
11. (h) Arai, S.; Hamaguchi, S.; Shioiri, T. Tetrahedron Lett. 1998, 39, 2997.
12. (i) Tanaka, K.; Watanabe, T.; Shimamoto, K.-Y.; Sahakitpichan, P.; Fuji, K. Tetrahedron Lett. 1999, 40, 6599.
13. (a) Rein, T.; Kann, N.; Kreuder, R.; Gangloff, B.; Reiser, O. Angew. Chem. 1994, 106, 597; Angew. Chem. Int., Ed. Engl. 1994, 33, 556.
14. (a) Rein, T.; Kann, N.; Kreuder, R.; Gangloff, B.; Reiser, O. Angew. Chem. 1994, 106, 597; Angew. Chem. Int., Ed. Engl. 1994, 33, 556.
15. (b) Rein, T.; Kreuder, R.; von Zezschwitz, P.; Wulff, C.; Reiser, O. Angew. Chem. 1995, 107, 1099; Angew. Chem., Int. Ed. Engl. 1995, 34, 1023.
16. (b) Rein, T.; Kreuder, R.; von Zezschwitz, P.; Wulff, C.; Reiser, O. Angew. Chem. 1995, 107, 1099; Angew. Chem., Int. Ed. Engl. 1995, 34, 1023.
17. (c) Rein, T.; Anvelt, J.; Soone, A.; Kreuder, R.; Wulff, C.; Reiser, O. Tetrahedron Lett. 1995, 36, 2303.
18. (d) Mendlik, M. T.; Cottard, M.; Rein, T.; Helquist, P. Tetrahedron Lett. 1997, 38, 6375.
19. (e) Kreuder, R.; Rein, T.; Reiser, O. Tetrahedron Lett. 1997, 38, 9035.
20. Norrby, P.-O.; Brandt, P.; Rein, T. J. Org. Chem. 1999, 64, 5845 and references therein.
21. All new compounds gave spectroscopic and analytical data in accordance with the proposed structures. For details regarding experimental procedures and compound characterization, see the Supporting Information.
22. (a) Tanner, D.; Wyatt, P.; Johansson, F.; Bertilsson, S.; Andersson, P. G. Acta Chem. Scand. 1999, 53, 263.
23. (b) Tanner, D.; Harden, A.; Johansson, F.; Wyatt, P.; Andersson, P. G. Acta Chem. Scand. 1996, 50, 361.
24. 4b under these reaction conditions. As pointed out by a reviewer, it would be advantageous to compare the enantiomeric purity and chemical yield of the recovered 1 for each entry listed in Table 1; however, due to the relative lability of the aldehyde, this has not been performed. The same reasoning applies to aldehydes 6 and 9, Table 2.
25. At most, trace amounts of (Z)-products were detected in the crude products. Compounds 4 and 5a/5b were readily separated and isolated in pure form by standard flash chromatography.
26. In the crude product, the ratio (R,E)-5a/(S,E)-5a was 97:3. After chromatography, (R,E)-5a was obtained as a single detected diastereomer in the indicated yield.
27. The yields in the HWE reactions are calculated on the amount of base used, since this is the limiting reagent. It should be noted that the yields based on the amount of aldehyde substrate in general are almost twice as high in the PKR experiments as in the individual kinetic resolutions using a single phosphonate reagent.
28. With the exception of (Z)-10 and (E)-10, which are only partially separable, products differing in alkene geometry could be readily separated by flash chromatography. For compounds 8 and 10, isomers having identical alkene geometry but opposite configuration at the allylic stereocenter are at best partially separable by chromatography.
29. (a) Tanikaga, R.; Jun, T. X.; Kaji, A. J. Chem. Soc., Perkin Trans. 1 1990, 1185, and references therein.
30. (b) Gatti, R. G. P.; Larsson, A. L. E.; Bäckvall, J.-E. J. Chem. Soc., Perkin Trans. 1 1997, 577 and references therein.
31. Pedersen, T. M.; Hansen, E. L.; Jensen, J. F.; Rein, T.; Tanner, D.; Helquist, P. Manuscript in preparation.