A highly enantioenriched, configurationally stable α-thioallyllithium compound and the stereochemical course of its electrophilic alkylation

Organic Letters

Volumn 1, Issue 13, 1999, Pages 2081-2083

  Marr, Felix ^a   Fröhlich, Roland ^a   Hoppe, Dieter ^a  

^a UNIVERSITY OF MÜNSTER   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0042263385     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol991134o     Document Type: Article

References (40)

1. Reviews: (a) Hoppe, D.; Hense, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 2282.
2. (b) Beak, P.; Basu, A.; Gallagher, D. J.; Park, J. S.; Thavumanavan, S. Acc. Chem. Res. 1996, 29, 552.
3. (c) Aggarwal, V. K. Angew. Chem., Int. Ed. Engl. 1994, 33, 175.
4. See references in reviews given in ret's 1a-c for relevant examples.
5. (a) Dress, R. K.; Rölle, T.; Hoffmann, R. W. Chem. Ber. 1995, 128, 673.
6. (b) Hoffmann, R. W.; Dress, R. K.; Ruhland, T.; Wenzel, A. Chem. Ber. 1995, 128, 861.
7. (c) Ahlbrecht, H.; Harbach, J.; Hoffmann, R. W.; Ruhland, T. Liebigs Ann. 1995, 211.
8. (a) Reich, H. J.; Dykstra, R. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1469.
9. (b) Reich, H. J.; Dykstra, R. R. J. Am. Chem. Soc. 1993, 115, 7041.
10. (c) Reich, H. J.; Kulicke, K. J. J. Am. Chem. Soc. 1995, 117, 6621.
11. (d) Reich, H. J.; Kulicke, K. J. J. Am. Chem. Soc. 1996, 118, 273.
12. (a) Ruhland, T.; Dress, R.; Hoffmann, R. W. Angew. Chem., Int. Ed. Engl. 1993, 32, 1467.
13. (b) Hoffmann, R. W.; Klute, W. Chem. Eur. J. 1996, 2, 694.
14. (c) See refs 3a,c and 4a.
15. Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323.
16. Hoppe, D.; Kaiser, B.; Stratmann, O.; Fröhlich, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 2784.
17. This carbamoyl moiety was chosen with the aim of smooth deprotection under mild conditions. O-Allyl N-monoalkylcarbamates were already converted to the N,C-dilithiated species and employed in synthesis, see: Hanko, R.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1981, 20, 127.
18. (a) Hackler, R. E.; Balko, T. W. J. Org. Chem. 1973, 38, 2106.
19. (b) Hayashi, T. Tetrahedron Lett. 1974, 15, 339.
20. (c) Nakai, T.; Shiono, H.; Okawara, M. Tetrahedron Lett. 1974, 15, 3625.
21. (d) Nakai, T.; Ari-Izumi, A. Tetrahedron Lett. 1976, 17, 2355.
22. (a) Harayama, H.; Kozera, T.; Kimura, M.; Tanaka, S.; Tamaru, Y. Chem. Lett. 1996, 543.
23. (b) Harayama, H.; Nagahama, T.; Kozera, T.; Kimura, M.; Fugami K.; Tanaka, S.; Tamaru, Y. Bull. Chem. Soc. Jpn. 1997, 70, 445.
24. Harayama reported low de values for the thermally activated rearrangement of 0-6-carvyl N-methylthiocarbamates, see ref 10b. However, the rearrangement of 0-allyl imidazolethiocarboxylic esters has been applied in the stereospecific synthesis of (a) ansamycin derivatives and (b) the oligosaccharide fragment of calicheamicin γ1α: (a) Schnur, R. C.; Corman, M. L. J. Org. Chem. 1994, 59, 2581.
25. (b) Nicolaou, K. C.; Groneberg, R. D. J. Am. Chem. Soc. 1990, 112, 4085.
26. (a) Asami, M.; Ishizaki, T.; Inoue, S. Tetrahedron: Asymmetry 1994, 5, 793.
27. (b) Bhuniya, D.; DattaGupta, A.; Singh. V. K. J. Org. Chem. 1996, 61, 6108.
28. (c) Södergren, M. J.; Andersson, P. G. J. Am. Chem. Soc. 1998, 120, 10760.
29. (a) Fukazawa, T.; Hashimoto, T. Tetrahedron: Asymmetry 1993, 4, 2323.
30. (b) Fukazawa, T.; Shimoji, Y.; Hashimoto, T. Tetrahedron: Asymmetry 1996, 6, 1649.
31. 3).
32. The slight loss of enantioenrichment is probably due to a nonconcerted rearrangement. Pd(II) catalysis of the rearrangement led here to marked loss of ee. Moreover. Pd(0) catalysis is assumed to follow a reaction pathway of dissociation, involving a stabilized allyl cation, and therefore should furnish racemic 5-esters. See ref 13b.
33. During the course of this research, a high-yielding protocol for the Pd(0)-catalyzed rearrangement of rac-O-allyl thiocarbamates under efficient desymmetrization by external chiral induction was published. One of three examples is the rearrangement of 0-(2-cyclohexenyl) N-methylthiocarbamate. See: Böhme, A.; Gais, H.-J. Tetrahedron: Asymmetry 1999, 10, 2511.
34. 13C NMR, IR, MS, and elemental analysis.
35. 3). mp = 79°C (cyclohexane)) were isolated as white crystals.
36. Crystals suitable for X-ray diffraction analyses were grown by vapor diffusion of pentane into an etheral solution of 10 or 11. (20) First example:
37. (a) Hoppe, D.; Zschage, O. Angew. Chem., Int. Ed. Engl. 1989, 28, 67.
38. (b) Revised configuration: Zschage, O.; Hoppe, D. Tetrahedron 1992, 48, 5657.
39. (c) Paulsen, H.; Graeve, C.; Hoppe, D. Synthesis 1996, 141.
40. Behrens, K.; Fröhlich, R.; Meyer, O.; Hoppe, D. Eur. J. Org. Chem. 1998, 2397.