Copper(I)-mediated highly stereoselective syn-carbometalation of secondary or tertiary propargylic alcohols with primary Grignard reagents in toluene with a high linear regioselectivity

Advanced Synthesis and Catalysis

Volumn 348, Issue 14, 2006, Pages 1894-1898

  Ma, Shengming ^a,b   Lu, Zhan ^a  

^a ZHEJIANG UNIVERSITY   (China)

^b SHANGHAI INSTITUTE OF ORGANIC CHEMISTRY   (China)

Author keywords

C C coupling; Copper; Grignard reagents; Kinetic resolution; Propargyl alcohols; Regioselectivity

Indexed keywords

EID: 33749321641     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200606004     Document Type: Article

References (43)

1. For an excellent review on carbometalation of alkynes, see: J. F. Normant, Synthesis 1981, 841.
2. For reviews on the synthesis of chiral proparylic alcohols, see: a) D. E. Frantz, R. Fassler, C. S. Tomooka, E. M. Carreira, Acc. Chem. Res. 2000, 33, 373;
3. b) Q. He, S. Ma, Chin. J. Org. Chem. 2002, 22, 375;
4. c) L. Pu, Tetrahedron 2003, 59, 9873.
5. a) M. Nakamura, C. Liang, E. Nakamura, Org. Lett. 2004, 6, 2015;
6. b) B. M. Trost, M. T. Rudd, 2002, 124, 4178;
7. c) B. M. Trost, S. Oi, J. Am. Chem. Soc. 2001, 123, 1230;
8. d) S. Ma, B. Wu, S. Zhao, Org. Lett. 2003, 5, 4429;
9. e) B. M. Trost, Z. T. Ball, T. Joge, Angew. Chem. Int. Ed. 2003, 42, 3415;
10. f) Y. Nishibayashi, Y. Inada, M. Yoshikawa, M. Hidai, S. Uemura, Angew. Chem. Int. Ed. 2003, 42, 1495;
11. g) Y. Nishibayashi, M. Yoshikawa, Y. Inada, M. D. Milton, M. Hidai, S. Uemura, Angew. Chem. Int. Ed. 2003, 42, 2681;
12. h) Y. Nishibayashi, Y. Inada, M. Hidai, S. Uemura, J. Am. Chem. Soc. 2003, 12, 6060.
13. A. G. Fallis, P. Forgione, Tetrahedron 2001, 57, 5899.
14. For carbometalation of propargylic alcohols with similar regioselectivity, see: a) J. G. Duboudin, B. Jousseaume, Synth. Commun. 1979, 9, 53;
15. b) J. G. Duboudin, B. Jousseaume, J. Organomet. Chem. 1979, 168, 1;
16. c) S. Ma, E. Negishi, J. Org. Chem. 1997, 62, 784;
17. for hydrometallation of propargylic alcohols with similar regioselectivity, see: d) E. J. Corey, J. A. Katzenellenbogen, G. S. Posner, J. Am. Chem. Soc. 1967, 89, 4245;
18. e) F. Sato, H. Ishikawa, H. Watanabe, K. Miyake, M. Sato, Chem. Commun. 1981, 718;
19. f) F. Sato, H. Watanabe, Y. Tanaka, M. Sato, Chem. Commun. 1982, 1126.
20. For carbometalation of propargylic ethers affording allenes, see: a) D. J. Nelson, W. J. Miller, J. Chem. Soc., Chem. Commun. 1973, 444;
21. b) J.-L. Moreau, M. Gaudemar, J. Organomet. Chem. 1976, 108, 159;
22. c) A. Alexakis, I. Marek, P. Mangeney, J. F. Normant, J. Am. Chem. Soc. 1990, 112, 8042.
23. a) J. F. Normant, A. Alexakis, J. Villieras, J. Organomet. Chem. 1973, 57, C99;
24. b) A. Alexakis, J. F. Normant, J. Villieras, J. Mol. Cat. 1975/76, 1, 43.
25. For the only example of hydroalumination of propargylic alcohols with a reversed regioselectivity, see: E. J. Corey, H. A. Kirst, J. A. Katzenellenbogen, J. Am. Chem. Soc. 1970, 92, 6314.
26. I. Creton, I. Marek, J. F. Normant, Synthesis 1996, 1499.
27. a) J. G. Duboudin, B. Jousseaume, A. Bonakdar, J. Organomet. Chem. 1979, 168, 227;
28. b) J. G. Duboudin, B. Jousseaume, J. Organomet. Chem. 1979, 168, 233.
29. P. E. Tessier, A. J. Penwell, F. E. S. Souza, G. A. Fallis, Org. Lett. 2003, 5, 2989.
30. a) K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahedron Lett. 1975, 4467;
31. b) A. Kollhofer, T. Pullmann, H. Plenio, Angew. Chem. Int. Ed. 2003, 42, 1056;
32. c) R. Tykwinski, Angew. Chem. Int. Ed. 2003, 42, 1566;
33. d) D. Gelman, S. Buchwald, Angew. Chem. Int. Ed. 2003, 42, 5993;
34. e) N. Sakai, K. Annaka, T. Konakahara, Org. Lett. 2004, 6, 1527;
35. f) S. Ma, H. Ren, Q. Wei, J. Am. Chem. Soc. 2003, 125, 4817.
36. a) K. Burgess, L. D. Jennings, J. Am. Chem. Soc. 1991, 113, 6129;
37. b) M. B. Onaran, C. T. Seto, J. Org. Chem. 2003, 68, 8136.
38. a) E. M. Anderson, K. M. Larsson, O. Kirk, Biocatal. Biotransform. 1998, 16, 181;
39. b) D. Xu, Z. Li, S. Ma, Chem. Eur. J. 2002, 21, 5012;
40. c) D. Xu, D.; Z. Li, S. Ma, Tetrahedron Lett. 2003, 44, 6343;
41. d) D. Xu, Z. Li, S. Ma, Tetrahedron: Asymmetry 2003, 14, 3657;
42. e) D. Xu, Z. Lu, Z. Li, S. Ma, Tetrahedron 2004, 60, 11870.
43. The sample of R-1a used in this study was purchased from Acros Organics.