The lithium-ene cyclization and the purported carbanion-induced ene cyclization [16]

Journal of the American Chemical Society

Volumn 121, Issue 43, 1999, Pages 10241-10242

  Cheng, Dai ^a   Zhu, Shirong ^a   Liu, Xiaojun ^a   Norton, Steven H ^a   Cohen, Theodore ^a  

^a UNIVERSITY OF PITTSBURGH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; LITHIUM;

CALCULATION; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONTROLLED STUDY; CYCLIZATION; LETTER; PROTON TRANSPORT; THERMODYNAMICS;

EID: 84961981775     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992583m     Document Type: Letter

References (31)

1. Taken in part from the M.S. Theses of Shirong Zhu (1997) and Xiaojun Liu (1999) and the Ph.D. Thesis of Steven H. Norton (1999) at the University of Pittsburgh.
2. Reviews of metallo-ene reactions: Oppolzer, W. Angew. Chem., Int. Ed. Engl. 1989, 28, 38-52. Oppolzer, W. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, England, 1991; Vol. 5, pp 29-61.
3. Reviews of metallo-ene reactions: Oppolzer, W. Angew. Chem., Int. Ed. Engl. 1989, 28, 38-52. Oppolzer, W. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, England, 1991; Vol. 5, pp 29-61.
4. The Zn-ene cyclization, used less extensively in synthesis, has recently come into prominence. Recent references: Nakamura, E.; Kubota, K. J. Org. Chem. 1997, 62, 792-793. Lorthiois, E.; Marek, I.; Normant, J.-F. J. Org. Chem. 1998, 63, 2442-50.
5. The Zn-ene cyclization, used less extensively in synthesis, has recently come into prominence. Recent references: Nakamura, E.; Kubota, K. J. Org. Chem. 1997, 62, 792-793. Lorthiois, E.; Marek, I.; Normant, J.-F. J. Org. Chem. 1998, 63, 2442-50.
6. Cyclization of nonallylic unsaturated organolithiums: Bailey, W. F.; Ovaska, T. V. In Advances in Detailed Reaction Mechanisms; Coxon, J. M., Ed.; JAI Press: Greenwich, CT, 1994; Vol. 3, pp 251-273.
7. Josey, A. D. J. Org. Chem. 1974, 39, 139-145.
8. 2 may be special cases: Klumpp, G. W.; Schmitz, R. F. Tetrahedron Lett. 1974, 2911-14 (strained enophile). Krief, A.; Derouane, D.; Dumont, W. Synlett 1992, 907-908 (1,1,3,3-tetrasubstituted allyllithium).
9. 2 may be special cases: Klumpp, G. W.; Schmitz, R. F. Tetrahedron Lett. 1974, 2911- 14 (strained enophile). Krief, A.; Derouane, D.; Dumont, W. Synlett 1992, 907-908 (1,1,3,3-tetrasubstituted allyllithium).
10. Cohen, T.; Bhupathy, M. Acc. Chem. Res. 1989, 22, 152-161.
11. 3) complexes. Fraenkel, G.; Cabral, J. A. J. Am. Chem. Soc. 1993, 115, 1551-1557.
12. A reviewer observed that the mainly cis configuration of 11 supports the metallo-ene cyclization since a trans configuration is generated when a nonallylic secondary organolithium cyclizes in a similar fashion: Bailey, W. F.; Nurmi, T. T.; Patricia, J. J.; Wang, W. J. Am. Chem. Soc. 1987, 109, 2442-48.
13. Edwards, J. H.; McQuillin, F. J. J. Chem. Soc., Chem. Commun. 1977, 838-839. See also: Cuvigny, T.; Julia, M.; Rolando, C. J. Organomet. Chem. 1988, 344, 9-28.
14. Edwards, J. H.; McQuillin, F. J. J. Chem. Soc., Chem. Commun. 1977, 838-839. See also: Cuvigny, T.; Julia, M.; Rolando, C. J. Organomet. Chem. 1988, 344, 9-28.
15. Bates, R. B.; Kroposki, L. M.; Potter, D. E. J. Org. Chem. 1972, 37, 560-562.
16. McElroy, B. J.; Merkley, J. H., U.S. Patent 3,678,121, July 18, 1972. Halasa, A. F., U.S. Patent 3,966,691, June 29, 1976. Quack, G.; Fetters, L. J. Macromolecules 1978, 11, 369-373.
17. McElroy, B. J.; Merkley, J. H., U.S. Patent 3,678,121, July 18, 1972. Halasa, A. F., U.S. Patent 3,966,691, June 29, 1976. Quack, G.; Fetters, L. J. Macromolecules 1978, 11, 369-373.
18. McElroy, B. J.; Merkley, J. H., U.S. Patent 3,678,121, July 18, 1972. Halasa, A. F., U.S. Patent 3,966,691, June 29, 1976. Quack, G.; Fetters, L. J. Macromolecules 1978, 11, 369-373.
19. Snider, B. B. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Paquette, L. A., Eds.; Pergamon: Oxford, 1991; Vol. 5, pp 1-25.
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21. See Supporting Information for details.
22. Gaussian 94, Revision B.2, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A.; Gaussian, Inc.: Pittsburgh, PA, 1995.
23. Full computations concerning these and related reactions will be published separately.
24. This and subsequent energy values are from Becke3-LYP/6-31G* calculations.
25. Miertus, S.; Scrocco, E.; Tomasi, J. Chem. Phys. 1981, 55, 117-129. Miertus, S.; Tomasi, J. Chem. Phys. 1982, 65, 239-245. Cossi, M.; Barone, V.; Cammi, R.; Tomasi, J. Chem. Phys. Lett. 1996, 255, 327-335.
26. Miertus, S.; Scrocco, E.; Tomasi, J. Chem. Phys. 1981, 55, 117-129. Miertus, S.; Tomasi, J. Chem. Phys. 1982, 65, 239-245. Cossi, M.; Barone, V.; Cammi, R.; Tomasi, J. Chem. Phys. Lett. 1996, 255, 327-335.
27. Miertus, S.; Scrocco, E.; Tomasi, J. Chem. Phys. 1981, 55, 117-129. Miertus, S.; Tomasi, J. Chem. Phys. 1982, 65, 239-245. Cossi, M.; Barone, V.; Cammi, R.; Tomasi, J. Chem. Phys. Lett. 1996, 255, 327-335.
28. Foresman, J. B.; Keith, T. A.; Wiberg, K. B.; Snoonian, J.; Frisch, M. J. J. Phys. Chem. 1996, 100, 16098-16104.
29. 17
30. Cheng, D.; Knox, K. R.; Cohen, T. Manuscript in preparation.
31. N′ reaction. Dieters, A.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1999, 38, 546-548.