A Valine-Derived Lithiated 3-Methylthiomethyl-1,3-oxazolidin-2-one for Enantioselective Nucleophilic Hydroxymethylation, Formylation, and Alkoxycarbonylation of Aldehydes

Organic Letters

Volumn 2, Issue 11, 2000, Pages 1501-1504

  Gaul, Christoph ^a   Seebach, Dieter ^a  

^a ETH ZURICH   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001401531     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0000410     Document Type: Article

References (33)

1. Part of the projected Ph.D. Thesis of C.G., ETH Zürich
2. Seebach, D. Angew. Chem., Int. Ed. Engl. 1979, 18, 239.
3. Some synthetic equivalents of chiral formyl anions used for simple carbonyl additions are deprotonated dithiane and dithiolane oxides (Scolastico Aggarwal) or certain lithiated α-heterosubstituted vinyllithium compounds (Braun). (a) Colombo, L.; Gennari, C.; Scolastico, G.; Guanti, G.; Narisano, E. J. Chem. Soc., Perkin Trans. 1 1981, 1278. (b) Aggarwal, V. K.; Thomas, A.; Schade, S. Tetrahedron 1997, 53, 16213. (c) Aggarwal, V. K.; Franklin, R.; Maddock, J.; Evans, G. R.; Thomas, A.; Mahon, M. F.; Molloy, K. C.; Rice, M. J. J. Org. Chem. 1995, 60, 2174. (d) Aggarwal, V. K.; Schade, S.; Adams, H. J. Org. Chem. 1997, 62, 1139. (e) Braun, M. Angew. Chem., Int. Ed. 1998, 37, 430. (f) Mahler, H.; Braun, M. Chem. Ber. 1991, 124, 1379.
4. Some synthetic equivalents of chiral formyl anions used for simple carbonyl additions are deprotonated dithiane and dithiolane oxides (Scolastico Aggarwal) or certain lithiated α-heterosubstituted vinyllithium compounds (Braun). (a) Colombo, L.; Gennari, C.; Scolastico, G.; Guanti, G.; Narisano, E. J. Chem. Soc., Perkin Trans. 1 1981, 1278. (b) Aggarwal, V. K.; Thomas, A.; Schade, S. Tetrahedron 1997, 53, 16213. (c) Aggarwal, V. K.; Franklin, R.; Maddock, J.; Evans, G. R.; Thomas, A.; Mahon, M. F.; Molloy, K. C.; Rice, M. J. J. Org. Chem. 1995, 60, 2174. (d) Aggarwal, V. K.; Schade, S.; Adams, H. J. Org. Chem. 1997, 62, 1139. (e) Braun, M. Angew. Chem., Int. Ed. 1998, 37, 430. (f) Mahler, H.; Braun, M. Chem. Ber. 1991, 124, 1379.
5. Some synthetic equivalents of chiral formyl anions used for simple carbonyl additions are deprotonated dithiane and dithiolane oxides (Scolastico Aggarwal) or certain lithiated α-heterosubstituted vinyllithium compounds (Braun). (a) Colombo, L.; Gennari, C.; Scolastico, G.; Guanti, G.; Narisano, E. J. Chem. Soc., Perkin Trans. 1 1981, 1278. (b) Aggarwal, V. K.; Thomas, A.; Schade, S. Tetrahedron 1997, 53, 16213. (c) Aggarwal, V. K.; Franklin, R.; Maddock, J.; Evans, G. R.; Thomas, A.; Mahon, M. F.; Molloy, K. C.; Rice, M. J. J. Org. Chem. 1995, 60, 2174. (d) Aggarwal, V. K.; Schade, S.; Adams, H. J. Org. Chem. 1997, 62, 1139. (e) Braun, M. Angew. Chem., Int. Ed. 1998, 37, 430. (f) Mahler, H.; Braun, M. Chem. Ber. 1991, 124, 1379.
6. Some synthetic equivalents of chiral formyl anions used for simple carbonyl additions are deprotonated dithiane and dithiolane oxides (Scolastico Aggarwal) or certain lithiated α-heterosubstituted vinyllithium compounds (Braun). (a) Colombo, L.; Gennari, C.; Scolastico, G.; Guanti, G.; Narisano, E. J. Chem. Soc., Perkin Trans. 1 1981, 1278. (b) Aggarwal, V. K.; Thomas, A.; Schade, S. Tetrahedron 1997, 53, 16213. (c) Aggarwal, V. K.; Franklin, R.; Maddock, J.; Evans, G. R.; Thomas, A.; Mahon, M. F.; Molloy, K. C.; Rice, M. J. J. Org. Chem. 1995, 60, 2174. (d) Aggarwal, V. K.; Schade, S.; Adams, H. J. Org. Chem. 1997, 62, 1139. (e) Braun, M. Angew. Chem., Int. Ed. 1998, 37, 430. (f) Mahler, H.; Braun, M. Chem. Ber. 1991, 124, 1379.
7. Some synthetic equivalents of chiral formyl anions used for simple carbonyl additions are deprotonated dithiane and dithiolane oxides (Scolastico Aggarwal) or certain lithiated α-heterosubstituted vinyllithium compounds (Braun). (a) Colombo, L.; Gennari, C.; Scolastico, G.; Guanti, G.; Narisano, E. J. Chem. Soc., Perkin Trans. 1 1981, 1278. (b) Aggarwal, V. K.; Thomas, A.; Schade, S. Tetrahedron 1997, 53, 16213. (c) Aggarwal, V. K.; Franklin, R.; Maddock, J.; Evans, G. R.; Thomas, A.; Mahon, M. F.; Molloy, K. C.; Rice, M. J. J. Org. Chem. 1995, 60, 2174. (d) Aggarwal, V. K.; Schade, S.; Adams, H. J. Org. Chem. 1997, 62, 1139. (e) Braun, M. Angew. Chem., Int. Ed. 1998, 37, 430. (f) Mahler, H.; Braun, M. Chem. Ber. 1991, 124, 1379.
8. Some synthetic equivalents of chiral formyl anions used for simple carbonyl additions are deprotonated dithiane and dithiolane oxides (Scolastico Aggarwal) or certain lithiated α-heterosubstituted vinyllithium compounds (Braun). (a) Colombo, L.; Gennari, C.; Scolastico, G.; Guanti, G.; Narisano, E. J. Chem. Soc., Perkin Trans. 1 1981, 1278. (b) Aggarwal, V. K.; Thomas, A.; Schade, S. Tetrahedron 1997, 53, 16213. (c) Aggarwal, V. K.; Franklin, R.; Maddock, J.; Evans, G. R.; Thomas, A.; Mahon, M. F.; Molloy, K. C.; Rice, M. J. J. Org. Chem. 1995, 60, 2174. (d) Aggarwal, V. K.; Schade, S.; Adams, H. J. Org. Chem. 1997, 62, 1139. (e) Braun, M. Angew. Chem., Int. Ed. 1998, 37, 430. (f) Mahler, H.; Braun, M. Chem. Ber. 1991, 124, 1379.
9. (a) Enders, D.; Bolkenius, M.; Vazquez, J.; Lassaletta, J. M.; Fernandez, R. J. Prakt. Chem. 1998, 340, 281.
10. (b) Pareja, C.; Martin-Zamora, E.; Fernandez, R.; Lassaletta, J. M. J. Org. Chem. 1999, 64, 8846.
11. (a) Eliel, E. L.; Morris-Natschke, S. J. Am. Chem. Soc. 1984, 106, 2937.
12. (b) Lynch, J. E.; Eliel, E. L. J. Am. Chew. Soc. 1984, 106, 2943.
13. (c) Ko, K. Y.; Frazee, W. J.; Eliel, E. L. Tetrahedron 1984, 40, 1333.
14. (d) Utimoto, K.; Nakamura, A.; Matsubara, S. J. Am. Chem. Soc. 1990, 112, 8189.
15. Kise, N.; Urai, T.; Yoshida, J. Tetrahedron: Asymmetry 1998, 9, 3125.
16. Hintermann, T.; Seebach, D. Helv. Chim. Acta 1998, 81, 2093.
17. See also independent work with this oxazolidinone by two other groups: (a) Bull, S. D.; Davies, S. G.; Jones, S.; Sanganee, H. J. J. Chem. Soc., Perkin Trans. 1 1999, 387. (b) Gibson, C. L.; Gillon, K.; Cook, S. Tetrahedron Lett. 1998, 39, 6733.
18. See also independent work with this oxazolidinone by two other groups: (a) Bull, S. D.; Davies, S. G.; Jones, S.; Sanganee, H. J. J. Chem. Soc., Perkin Trans. 1 1999, 387. (b) Gibson, C. L.; Gillon, K.; Cook, S. Tetrahedron Lett. 1998, 39, 6733.
19. Oxazolidinone 1 and its enantiomer are commercially available as (S)- and (R)-DIOZ: Shiratori Pharmaceutical Co., Ltd., Japan. Isobe, T.; Fukuda, K. Japanese Patent JP 09143173, 1995; Chem. Abstr. 1997, 127, 50635.
20. For a recent application in the synthesis of γ-amino acid derivatives, see: Brenner, M.; Seebach, D. Helv. Chim. Acta 1999, 82, 2365.
21. For reagents generated from carbonyl compounds with sterically protected but electronically effective C=O groups, see for instance: (a) Ertas, M.; Seebach, D. Helv. Chim. Acta 1985, 68, 961. (b) Lubosch, W.; Seebach, D. Helv. Chim. Acta 1980, 63, 102. (c) Schlecker, R.; Seebach, D. Helv. Chim. Acta 1977, 60, 1459. (d) Seebach, D.; Lubosch, W.; Enders, D. Chem. Ber. 1976, 109, 1309.
22. For reagents generated from carbonyl compounds with sterically protected but electronically effective C=O groups, see for instance: (a) Ertas, M.; Seebach, D. Helv. Chim. Acta 1985, 68, 961. (b) Lubosch, W.; Seebach, D. Helv. Chim. Acta 1980, 63, 102. (c) Schlecker, R.; Seebach, D. Helv. Chim. Acta 1977, 60, 1459. (d) Seebach, D.; Lubosch, W.; Enders, D. Chem. Ber. 1976, 109, 1309.
23. For reagents generated from carbonyl compounds with sterically protected but electronically effective C=O groups, see for instance: (a) Ertas, M.; Seebach, D. Helv. Chim. Acta 1985, 68, 961. (b) Lubosch, W.; Seebach, D. Helv. Chim. Acta 1980, 63, 102. (c) Schlecker, R.; Seebach, D. Helv. Chim. Acta 1977, 60, 1459. (d) Seebach, D.; Lubosch, W.; Enders, D. Chem. Ber. 1976, 109, 1309.
24. For reagents generated from carbonyl compounds with sterically protected but electronically effective C=O groups, see for instance: (a) Ertas, M.; Seebach, D. Helv. Chim. Acta 1985, 68, 961. (b) Lubosch, W.; Seebach, D. Helv. Chim. Acta 1980, 63, 102. (c) Schlecker, R.; Seebach, D. Helv. Chim. Acta 1977, 60, 1459. (d) Seebach, D.; Lubosch, W.; Enders, D. Chem. Ber. 1976, 109, 1309.
25. The structure of 3 is drawn arbitrarily; the configuration of the lithiated carbon is unknown. Cf. the X-ray crystal structure of a 1-bromomagnesio-2-pivaloyltetrahydroisoquinoline: Seebach, D.; Hansen, J.; Seiler, P.; Gromek, J. M. J. Organomet. Chem. 1985, 285, 1.
26. (a) Pearson, W. H.; Lindbeck, A. C.; Kampf, J. W. J. Am. Chem. Soc. 1993, 115, 2622 and earlier references therein.
27. (b) Tomoyasu, T.; Tomooka, K.; Nakai, T. Synlett 1998, 1147.
28. (c) Tomoyasu, T.; Tomooka, K.; Nakai, T. Tetrahedron Lett. 2000, 41, 345.
29. All compounds were fully characterized by physical and chemical data.
30. This model is consistent with observations made by Pearson and Nakai (cf. ref 13).
31. 2) to give 6 (557 mg, 77%) as a 98.5:1.5 mixture with its C(2′)-OH epimer.
32. For oxazolidinone-based hemiaminals, see: Bach, J.; Bull, S. D.; Davies, S. G.; Nicholson, A. D. Tetrahedron Lett. 1999, 40, 6677.
33. 4) and concentrated under reduced pressure. Purification by flash chromatography, eluting with pentane/AcOEt (4:1), afforded 10a (151 mg, 90%) as a colorless oil.