Facile enantioselective synthesis of propargylic alcohols by direct addition of terminal alkynes to aldehydes [3]

Journal of the American Chemical Society

Volumn 122, Issue 8, 2000, Pages 1806-1807

  Frantz, Doug E ^a   Fässler, Roger ^a   Carreira, Erick M ^a  

^a ETH ZURICH   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; ALDEHYDE DERIVATIVE; ALKYNE DERIVATIVE;

CHEMICAL BOND; CHEMICAL STRUCTURE; ENANTIOMER; LETTER; OPTICAL ROTATION; REACTION ANALYSIS; SYNTHESIS;

EID: 0041407526     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993838z     Document Type: Letter

References (29)

1. For selected examples of the use of optically active propargylic alcohols in synthesis, see: (a) Marshall, J. A.; Wang, X. J. J. Org. Chem. 1992, 57, 1242. (b) Roush, W. R.; Sciotti, R. J. J. Am. Chem. Soc. 1994, 116, 6457. (c) Myers, A. G.; Zheng, B. J. Am. Chem. Soc. 1996, 118, 4492.
2. For selected examples of the use of optically active propargylic alcohols in synthesis, see: (a) Marshall, J. A.; Wang, X. J. J. Org. Chem. 1992, 57, 1242. (b) Roush, W. R.; Sciotti, R. J. J. Am. Chem. Soc. 1994, 116, 6457. (c) Myers, A. G.; Zheng, B. J. Am. Chem. Soc. 1996, 118, 4492.
3. For selected examples of the use of optically active propargylic alcohols in synthesis, see: (a) Marshall, J. A.; Wang, X. J. J. Org. Chem. 1992, 57, 1242. (b) Roush, W. R.; Sciotti, R. J. J. Am. Chem. Soc. 1994, 116, 6457. (c) Myers, A. G.; Zheng, B. J. Am. Chem. Soc. 1996, 118, 4492.
4. Stoichiometric ketone reductions: (a) Midland, M. M.; Tramontano, A.; Zderic, S. A. J. Am. Chem. Soc. 1977, 99, 5211. (b) Yamaguchi, S.; Mosher, H. S.; Pohland, A. J. Am. Chem. Soc. 1972, 94, 9254. (c) Mishizawa, M.; Yamada, M.; Noyori, R. Tetrahedron Lett. 1981, 22, 247. (d) Brown, H. C.; Ramachandran, P. V. Acc. Chem. Res. 1992, 25, 16. (e) Bach, J.; Berenguer, R.; Garcia, J.; Loscertales, T.; Vilarrasa, J. J. Org. Chem. 1996, 61, 9021.
5. Stoichiometric ketone reductions: (a) Midland, M. M.; Tramontano, A.; Zderic, S. A. J. Am. Chem. Soc. 1977, 99, 5211. (b) Yamaguchi, S.; Mosher, H. S.; Pohland, A. J. Am. Chem. Soc. 1972, 94, 9254. (c) Mishizawa, M.; Yamada, M.; Noyori, R. Tetrahedron Lett. 1981, 22, 247. (d) Brown, H. C.; Ramachandran, P. V. Acc. Chem. Res. 1992, 25, 16. (e) Bach, J.; Berenguer, R.; Garcia, J.; Loscertales, T.; Vilarrasa, J. J. Org. Chem. 1996, 61, 9021.
6. Stoichiometric ketone reductions: (a) Midland, M. M.; Tramontano, A.; Zderic, S. A. J. Am. Chem. Soc. 1977, 99, 5211. (b) Yamaguchi, S.; Mosher, H. S.; Pohland, A. J. Am. Chem. Soc. 1972, 94, 9254. (c) Mishizawa, M.; Yamada, M.; Noyori, R. Tetrahedron Lett. 1981, 22, 247. (d) Brown, H. C.; Ramachandran, P. V. Acc. Chem. Res. 1992, 25, 16. (e) Bach, J.; Berenguer, R.; Garcia, J.; Loscertales, T.; Vilarrasa, J. J. Org. Chem. 1996, 61, 9021.
7. Stoichiometric ketone reductions: (a) Midland, M. M.; Tramontano, A.; Zderic, S. A. J. Am. Chem. Soc. 1977, 99, 5211. (b) Yamaguchi, S.; Mosher, H. S.; Pohland, A. J. Am. Chem. Soc. 1972, 94, 9254. (c) Mishizawa, M.; Yamada, M.; Noyori, R. Tetrahedron Lett. 1981, 22, 247. (d) Brown, H. C.; Ramachandran, P. V. Acc. Chem. Res. 1992, 25, 16. (e) Bach, J.; Berenguer, R.; Garcia, J.; Loscertales, T.; Vilarrasa, J. J. Org. Chem. 1996, 61, 9021.
8. Stoichiometric ketone reductions: (a) Midland, M. M.; Tramontano, A.; Zderic, S. A. J. Am. Chem. Soc. 1977, 99, 5211. (b) Yamaguchi, S.; Mosher, H. S.; Pohland, A. J. Am. Chem. Soc. 1972, 94, 9254. (c) Mishizawa, M.; Yamada, M.; Noyori, R. Tetrahedron Lett. 1981, 22, 247. (d) Brown, H. C.; Ramachandran, P. V. Acc. Chem. Res. 1992, 25, 16. (e) Bach, J.; Berenguer, R.; Garcia, J.; Loscertales, T.; Vilarrasa, J. J. Org. Chem. 1996, 61, 9021.
9. Catalytic ketone reductions: (a) Helal, C. J.; Magriotis, P. A.; Corey, E. J. J. Am. Chem. Soc. 1996, 118, 10938. (b) Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1997, 119, 8738. (c) Parker, K. A.; Ledeboer, M. W. J. Org. Chem. 1996, 61, 3214.
10. Catalytic ketone reductions: (a) Helal, C. J.; Magriotis, P. A.; Corey, E. J. J. Am. Chem. Soc. 1996, 118, 10938. (b) Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1997, 119, 8738. (c) Parker, K. A.; Ledeboer, M. W. J. Org. Chem. 1996, 61, 3214.
11. Catalytic ketone reductions: (a) Helal, C. J.; Magriotis, P. A.; Corey, E. J. J. Am. Chem. Soc. 1996, 118, 10938. (b) Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1997, 119, 8738. (c) Parker, K. A.; Ledeboer, M. W. J. Org. Chem. 1996, 61, 3214.
12. Corey, E. J.; Cimprich, K. A. J. Am. Chem. Soc. 1994, 116, 3151.
13. For the asymmetric addition of lithium and magnesium acetylides to trifluoromethyl aryl ketones, see: (a) Tan, L.; Chen, C.-Y.; Tillyer, R. D.; Grabowski, E. J. J.; Reider, P. Angew. Chem., Int. Ed. 1999, 38, 711. (b) For a recent report on the addition of aromatic aldehydes with alkynylzinc reagents generated in situ from terminal acetylenes and dimethylzinc, see; Li, Z.; Upadhyay, V.; DeCamp, A. E.; DiMichele, L.; Reider, P. J. Synthesis 1999, 1453. (c) For the enantioselective addition of zinc acetylides (generated from the corresponding lithium acetylides) to aldehydes, see: Niwa, S.; Soai, K. J. Chem Soc., Perkin Trans. 1 1990, 937. Tombo, G. M. R.; Didier, E.; Loubinoux, B. Synlett 1990, 547.
14. For the asymmetric addition of lithium and magnesium acetylides to trifluoromethyl aryl ketones, see: (a) Tan, L.; Chen, C.-Y.; Tillyer, R. D.; Grabowski, E. J. J.; Reider, P. Angew. Chem., Int. Ed. 1999, 38, 711. (b) For a recent report on the addition of aromatic aldehydes with alkynylzinc reagents generated in situ from terminal acetylenes and dimethylzinc, see; Li, Z.; Upadhyay, V.; DeCamp, A. E.; DiMichele, L.; Reider, P. J. Synthesis 1999, 1453. (c) For the enantioselective addition of zinc acetylides (generated from the corresponding lithium acetylides) to aldehydes, see: Niwa, S.; Soai, K. J. Chem Soc., Perkin Trans. 1 1990, 937. Tombo, G. M. R.; Didier, E.; Loubinoux, B. Synlett 1990, 547.
15. For the asymmetric addition of lithium and magnesium acetylides to trifluoromethyl aryl ketones, see: (a) Tan, L.; Chen, C.-Y.; Tillyer, R. D.; Grabowski, E. J. J.; Reider, P. Angew. Chem., Int. Ed. 1999, 38, 711. (b) For a recent report on the addition of aromatic aldehydes with alkynylzinc reagents generated in situ from terminal acetylenes and dimethylzinc, see; Li, Z.; Upadhyay, V.; DeCamp, A. E.; DiMichele, L.; Reider, P. J. Synthesis 1999, 1453. (c) For the enantioselective addition of zinc acetylides (generated from the corresponding lithium acetylides) to aldehydes, see: Niwa, S.; Soai, K. J. Chem Soc., Perkin Trans. 1 1990, 937. Tombo, G. M. R.; Didier, E.; Loubinoux, B. Synlett 1990, 547.
16. For the asymmetric addition of lithium and magnesium acetylides to trifluoromethyl aryl ketones, see: (a) Tan, L.; Chen, C.-Y.; Tillyer, R. D.; Grabowski, E. J. J.; Reider, P. Angew. Chem., Int. Ed. 1999, 38, 711. (b) For a recent report on the addition of aromatic aldehydes with alkynylzinc reagents generated in situ from terminal acetylenes and dimethylzinc, see; Li, Z.; Upadhyay, V.; DeCamp, A. E.; DiMichele, L.; Reider, P. J. Synthesis 1999, 1453. (c) For the enantioselective addition of zinc acetylides (generated from the corresponding lithium acetylides) to aldehydes, see: Niwa, S.; Soai, K. J. Chem Soc., Perkin Trans. 1 1990, 937. Tombo, G. M. R.; Didier, E.; Loubinoux, B. Synlett 1990, 547.
17. For other methods see: (a) Kobayashi, S.; Furuya, M.; Ohtsubo, A.; Mukaiyama, T. Tetrahedron: Asymmetry 1991, 2, 635. (b) Carreira, E. M.; Singer, R. A.; Lee, W. J. Am. Chem. Soc. 1994, 116, 8837. (c) Singer, R. A.; Shepard, M. S.; Carreira E. M. Tetrahedron 1998, 54, 7025.
18. For other methods see: (a) Kobayashi, S.; Furuya, M.; Ohtsubo, A.; Mukaiyama, T. Tetrahedron: Asymmetry 1991, 2, 635. (b) Carreira, E. M.; Singer, R. A.; Lee, W. J. Am. Chem. Soc. 1994, 116, 8837. (c) Singer, R. A.; Shepard, M. S.; Carreira E. M. Tetrahedron 1998, 54, 7025.
19. For other methods see: (a) Kobayashi, S.; Furuya, M.; Ohtsubo, A.; Mukaiyama, T. Tetrahedron: Asymmetry 1991, 2, 635. (b) Carreira, E. M.; Singer, R. A.; Lee, W. J. Am. Chem. Soc. 1994, 116, 8837. (c) Singer, R. A.; Shepard, M. S.; Carreira E. M. Tetrahedron 1998, 54, 7025.
20. Carreira, E. M.; Lee, W.; Singer, R. A. J. Am. Chem. Soc. 1995, 117, 3649.
21. (b) Ledford, B. E.; Carreira, E. M. Tetrahedron Lett. 1997, 38, 8125.
22. (c) Gauthier, D. R., Jr.; Carreira, E. M. Angew. Chem., Int. Ed. Engl. 1996, 35, 2363.
23. (a) Corey, E. J.; Cheng, X.-M. The Logic of Chemical Synthesis; Wiley: New York, 1989.
24. (b) Hendrickson, J. B. J. Am. Chem. Soc. 1977, 99, 5439.
25. 13C NMR data: Frantz, D. E.; Fässler, R.; Carreira, E. M. J. Am. Chem. Soc. 1999, 121, 11245.
26. The analogy to Cu chemistry has its limitations, however, as Cu-alkynylides do not normally undergo nucleophilic additions to aldehydes.
27. We have observed that unbranched n-aliphatic aldehydes give products in slightly lower % ee's, albeit in modest yields. For example, the addition of phenylacetylene to hexanal furnishes the corresponding adduct in 88% ee and 50% yield. The remaining aldehyde is consumed in the formation of self-condensation aldol products, as determined by mass balance. As seen in Table 2, aldehydes with either α- or β- substitution participate as excellent substrates in the addition reaction.
28. Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley: New York, 1994, Chapter 5.
29. In preliminary studies we have observed that the process displays positive nonlinear behavior. Thus, when 4-phenyl-1-butyne was added to cyclohexanecarboxaldehyde in the presence of N-methylephedrine (20% ee), the resulting propargylic alcohol was isolated in 39% ee.