Catalytic, enantioselective acetate aldol additions to α,β-ynals: Preparation of optically active propargylic alcohols

Tetrahedron

Volumn 54, Issue 25, 1998, Pages 7025-7032

  Singer, Robert A ^a   Shepard, Mary S ^a   Carreira, Erick M ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL;

ARTICLE; CATALYSIS; CYCLIZATION; METHODOLOGY; OPTICAL ROTATION; PRIORITY JOURNAL; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0032543738     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(98)00344-5     Document Type: Article

References (40)

1. 1. For selected recent examples of the use of optically active propargylic alcohols in synthesis, see: a) Johnson, W. S.; Frei, B.; Gopalan, A. S. J. Org. Chem. 1981, 46, 1512.
2. (b) Midland, M. M.; Tramontane, A. Tetrahedron Lett. 1980, 21, 3549.
3. (c) Midland, M. M.; Nguyen, N. H. J. Org. Chem. 1981, 46, 4107.
4. (d) Trost, B. M.; Hipskind, P. A.; Chung, J. Y. L.; Chan, C. Angew. Chem. 1989, 101, 1559; Angew. Chem., Int. Ed. Engl. 1989, 28, 1502.
5. (d) Trost, B. M.; Hipskind, P. A.; Chung, J. Y. L.; Chan, C. Angew. Chem. 1989, 101, 1559; Angew. Chem., Int. Ed. Engl. 1989, 28, 1502.
6. (e) Marshall, J. A.; Wang, X. J. J. Org. Chem. 1992, 57, 1242.
7. (e) Wender, P. A.; Ihle, N. C.; Correia, C. R. D. J. Am. Chem. Soc. 1988, 110, 5904.
8. 2. For reviews on stereocontrol in the synthesis of stereochemically complex acyclic systems, see: a) Bartlett, P. A. Tetrahedron 1980, 36, 2.
9. (b) Hoffmann, R. W. Chem. Rev. 1989, 89, 1841.
10. 3. For a general review of acetylene chemistry, see: Chemistry of the Carbon-Carbon Triple Bond, Patai, S., Ed.; Wiley: New York, 1978.
11. 4. Normant, J. F.; Alexakis, A. Synthesis, 1981, 841.
12. 5. Myers, A. G.; Zheng, B. J. Am. Chem. Soc. 1996, 118, 4492.
13. 6. (a) Carreira, E. M.; Hastings, C. A.; Shepard, M. S.; Yerkey, L. A.; Millward, D. B. J. Am. Chem. Soc. 1994, 116, 6622.
14. (b) Shepard, M. S.; Carreira, E. M. J. Am. Chem. Soc. 1997, 119, 2597.
15. (c) Shepard, M. S.; Carreira, E. M. Tetrahedron 1997, 55, 16253.
16. 7. Midland, M. M.; Tramontano, A.; Zderic, S. A. J. Am. Chem. Soc. 1977, 99, 5211.
17. 8. Yamaguchi, S.; Mosher, H. S.; Pohland, A. J. Am. Chem. Soc. 1972, 94, 9254.
18. 9. Brinkmeyer, R. S.; Kapoor, V. M. J. Am. Chem. Soc. 1977, 99, 8339.
19. 10. Midland, M. M.; Kazubski, A.; Woodling, R.E. J. Org. Chem. 1991, 56, 1068.
20. 11. Mishizawa, M.; Yamada, M.; Noyori, R. Tetrahedron Lett. 1981, 22, 247.
21. 12. Brown, H. C; Ramachandran, P. V. Acc. Chem. Res. 1992, 25, 16.
22. 13. Helal, C. J.; Magriotis, P. A.; Corey, E. J. J. Am. Chem. Soc. 1997, 118, 10938.
23. 14. Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1997, 119, 8738.
24. 15. Schmidt, B.; Seebach, D. Angew. Chem. 1991, 103, 1383; Angew. Chem., Int. Ed. Engl. 1991, 30, 1321.
25. 15. Schmidt, B.; Seebach, D. Angew. Chem. 1991, 103, 1383; Angew. Chem., Int. Ed. Engl. 1991, 30, 1321.
26. 16. Corey, E. J.; Cimprich, K. A. J. Am. Chem. Soc. 1994, 116, 3151.
27. 17. Kobayashi, S.; Furuya, M.; Ohtsubo, A.; Mukaiyama, T. Tetrahedron: Asymmetry 1991, 2, 635.
28. 18. The addition of 2-methoxypropene to alkynyl aldehydes to give acetone-aldol adducts has recently been reported, see: Carreira, E. M.; Lee, W.; Singer, R. A. J. Am. Chem. Soc. 1995, 117, 3649.
29. 19. Carreira, E. M.; Singer, R. A.; Lee, W. J. Am. Chem. Soc. 1994, 116, 8837.
30. 20. The structure of the active catalyst has not yet been determined. The illustrated structures of the Ti(IV) complexes are intended to indicate the putative catalyst composition.
31. 3 solution (R)-(+)-7 (Scheme 2) is isolated in 98% ee and 80% yield. A single recrystallization from benzene then furnishes (R)-(+)-7 in 99% ee; a second recrystallization provides (R)-(+)-7 in >99% ee. Since both (R)-(-)-and (S)-(+)-camphorsulfonic acids are inexpensive and readily available either (R)-(+)-or (S)-(-)-7 can be prepared employing the resolution procedure described.
32. 22. Recently, we have found that the catalytic, enantioselective acetate-aldol additions can be conducted with as little as 0.5 mol% 3; these results will be reported at a later time.
33. 23. The alkynyl aldehydes used in this study were prepared by treatment of the corresponding lithium acetylides with ethyl formate at -78 °C.
34. 24. Prepared according to the procedure of Kita, Y.; Segawa, J.; Haruta, J.; Yasuda, H.; Tamura, Y. J. Chem. Soc., Perkin Trans I, 1982, 1099.
35. 25. Dale, J. A.; Mosher, H. S. J. Am. Chem. Soc. 1973, 95, 512.
36. 2/Pd) to the corresponding known saturated ester.
37. D = +18.6, Tannabe, T.; Izumi, Y. Bull. Chem. Soc. Jpn. 1973, 46, 1550). (formula presented)
38. 27. (a) Lautens, M.; Delanghe, P. H. M. J. Am. Chem. Soc. 1994, 116, 8526.
39. (b) Marshall, J. A.; Tang, Y. J. Org. Chem. 1993, 58, 3233.
40. 28. Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923.