Cyclization by intramolecular carbolithiation of alkyl- and vinyllithiums prepared by reductive lithiation: Surprising stereochemistry in the lithium oxyanion accelerated cyclization

Journal of the American Chemical Society

Volumn 124, Issue 41, 2002, Pages 12106-12107

  Deng, Kai ^a   Bensari, Ahlem ^a   Cohen, Theodore ^a  

^a UNIVERSITY OF PITTSBURGH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; LITHIUM DERIVATIVE; VINYL DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; STEREOCHEMISTRY;

EID: 0037120914     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja027988c     Document Type: Article

References (25)

1. (a) Reviews: Bailey, W. F.; Ovaska, T. V. In Advances in Detailed Reaction Mechanisms; Coxon, J. M., Ed.; JAI Press: Greenwich, CT.; Vol. 3, 1994; p 251-273. Mealy, M. J.; Bailey, W. F. J. Organomet. Chem. 2002, 646, 59-67. Clayden, J. Organolithiums: Selectivity for Synthesis; Pergamon Press: New York, 2002; pp 293-335. The earliest reports of such cyclizations involved Grignard reagents and are due to the pioneering work of Richey: (b) Richey, H. G., Jr.; Rees, T. C. Tetrahedron Lett. 1966, 36, 4297-4301. Kossa, W. C., Jr.; Rees, T. C.; Richey, H. G., Jr. Tetrahedron Lett. 1971, 3455-3458.
2. (a) Reviews: Bailey, W. F.; Ovaska, T. V. In Advances in Detailed Reaction Mechanisms; Coxon, J. M., Ed.; JAI Press: Greenwich, CT.; Vol. 3, 1994; p 251-273. Mealy, M. J.; Bailey, W. F. J. Organomet. Chem. 2002, 646, 59-67. Clayden, J. Organolithiums: Selectivity for Synthesis; Pergamon Press: New York, 2002; pp 293-335. The earliest reports of such cyclizations involved Grignard reagents and are due to the pioneering work of Richey: (b) Richey, H. G., Jr.; Rees, T. C. Tetrahedron Lett. 1966, 36, 4297-4301. Kossa, W. C., Jr.; Rees, T. C.; Richey, H. G., Jr. Tetrahedron Lett. 1971, 3455-3458.
3. (a) Reviews: Bailey, W. F.; Ovaska, T. V. In Advances in Detailed Reaction Mechanisms; Coxon, J. M., Ed.; JAI Press: Greenwich, CT.; Vol. 3, 1994; p 251-273. Mealy, M. J.; Bailey, W. F. J. Organomet. Chem. 2002, 646, 59-67. Clayden, J. Organolithiums: Selectivity for Synthesis; Pergamon Press: New York, 2002; pp 293-335. The earliest reports of such cyclizations involved Grignard reagents and are due to the pioneering work of Richey: (b) Richey, H. G., Jr.; Rees, T. C. Tetrahedron Lett. 1966, 36, 4297-4301. Kossa, W. C., Jr.; Rees, T. C.; Richey, H. G., Jr. Tetrahedron Lett. 1971, 3455-3458.
4. (a) Reviews: Bailey, W. F.; Ovaska, T. V. In Advances in Detailed Reaction Mechanisms; Coxon, J. M., Ed.; JAI Press: Greenwich, CT.; Vol. 3, 1994; p 251-273. Mealy, M. J.; Bailey, W. F. J. Organomet. Chem. 2002, 646, 59-67. Clayden, J. Organolithiums: Selectivity for Synthesis; Pergamon Press: New York, 2002; pp 293-335. The earliest reports of such cyclizations involved Grignard reagents and are due to the pioneering work of Richey: (b) Richey, H. G., Jr.; Rees, T. C. Tetrahedron Lett. 1966, 36, 4297-4301. Kossa, W. C., Jr.; Rees, T. C.; Richey, H. G., Jr. Tetrahedron Lett. 1971, 3455-3458.
5. (a) Reviews: Bailey, W. F.; Ovaska, T. V. In Advances in Detailed Reaction Mechanisms; Coxon, J. M., Ed.; JAI Press: Greenwich, CT.; Vol. 3, 1994; p 251-273. Mealy, M. J.; Bailey, W. F. J. Organomet. Chem. 2002, 646, 59-67. Clayden, J. Organolithiums: Selectivity for Synthesis; Pergamon Press: New York, 2002; pp 293-335. The earliest reports of such cyclizations involved Grignard reagents and are due to the pioneering work of Richey: (b) Richey, H. G., Jr.; Rees, T. C. Tetrahedron Lett. 1966, 36, 4297-4301. Kossa, W. C., Jr.; Rees, T. C.; Richey, H. G., Jr. Tetrahedron Lett. 1971, 3455-3458.
6. Reviews: Cohen, T.; Bhupathy, M. Acc. Chem. Res. 1989, 22, 152-161. Cohen, T. In Heteroatom Chemistry; Block, E., Ed.; VCH Publishers: New York, 1990; Chapter 7, pp 129-142. For a review of the special method that uses a catalytic amount of the aromatic and a large excess of lithium, see Ramón, D. J.; Yus, M. Eur. J. Org. Chem. 2000, 225-237.
7. Reviews: Cohen, T.; Bhupathy, M. Acc. Chem. Res. 1989, 22, 152-161. Cohen, T. In Heteroatom Chemistry; Block, E., Ed.; VCH Publishers: New York, 1990; Chapter 7, pp 129-142. For a review of the special method that uses a catalytic amount of the aromatic and a large excess of lithium, see Ramón, D. J.; Yus, M. Eur. J. Org. Chem. 2000, 225-237.
8. Reviews: Cohen, T.; Bhupathy, M. Acc. Chem. Res. 1989, 22, 152-161. Cohen, T. In Heteroatom Chemistry; Block, E., Ed.; VCH Publishers: New York, 1990; Chapter 7, pp 129-142. For a review of the special method that uses a catalytic amount of the aromatic and a large excess of lithium, see Ramón, D. J.; Yus, M. Eur. J. Org. Chem. 2000, 225-237.
9. The only other examples of intramolecular carbolithiation of nonconjugated alkyllithiums prepared by reductive lithiation are by (a) Broka, C. A.; Shen, T. J. Am. Chem. Soc. 1989, 111, 2981-84, in which phenyl thioethers are substrates (two examples), (b) Rychnovsky, S. D.; Hata, T.; Kim, A. I.; Buckmelter, A. J. Org. Lett. 2001, 3, 807-810, in which a nitrile was the substrate (one example), and (c) Yus, M.; Ortiz, R.; Huerta, F. F. Tetrahedron Lett. 2002, 43, 2957-2960, in which an alkyl chloride was the substrate. In 3c, very special conditions were required for the tertiary case. References 3a and 3b appeared after we had completed much of our work described herein.
10. The only other examples of intramolecular carbolithiation of nonconjugated alkyllithiums prepared by reductive lithiation are by (a) Broka, C. A.; Shen, T. J. Am. Chem. Soc. 1989, 111, 2981-84, in which phenyl thioethers are substrates (two examples), (b) Rychnovsky, S. D.; Hata, T.; Kim, A. I.; Buckmelter, A. J. Org. Lett. 2001, 3, 807-810, in which a nitrile was the substrate (one example), and (c) Yus, M.; Ortiz, R.; Huerta, F. F. Tetrahedron Lett. 2002, 43, 2957-2960, in which an alkyl chloride was the substrate. In 3c, very special conditions were required for the tertiary case. References 3a and 3b appeared after we had completed much of our work described herein.
11. The only other examples of intramolecular carbolithiation of nonconjugated alkyllithiums prepared by reductive lithiation are by (a) Broka, C. A.; Shen, T. J. Am. Chem. Soc. 1989, 111, 2981-84, in which phenyl thioethers are substrates (two examples), (b) Rychnovsky, S. D.; Hata, T.; Kim, A. I.; Buckmelter, A. J. Org. Lett. 2001, 3, 807-810, in which a nitrile was the substrate (one example), and (c) Yus, M.; Ortiz, R.; Huerta, F. F. Tetrahedron Lett. 2002, 43, 2957-2960, in which an alkyl chloride was the substrate. In 3c, very special conditions were required for the tertiary case. References 3a and 3b appeared after we had completed much of our work described herein.
12. 3c reported one tertiary example each by reductive lithiation of, respectively, a nitrile and a chloride.
13. Bailey, W. F.; Nurmi, T. T.; Patricia, J. J.; Wang, W. J. Am. Chem. Soc. 1987, 109, 2442-2448. This lone secondary example proceeded in only 44% yield.
14. Cohen T.; Doubleday, M. D. J. Org. Chem. 1990, 55, 4784-86.
15. Use of Montmorillonite clay for the production of 3: Labiad, B.; Villemin, D. Synthesis 1989, 143-44; use of a cuprate for regiocontrol in the allylation: Giner, J. L.; Margot, C.; Djerassi, C. J. Org. Chem. 1989, 54, 2117-2125.
16. Use of Montmorillonite clay for the production of 3: Labiad, B.; Villemin, D. Synthesis 1989, 143-44; use of a cuprate for regiocontrol in the allylation: Giner, J. L.; Margot, C.; Djerassi, C. J. Org. Chem. 1989, 54, 2117-2125.
17. Cyclization of the cyclohexenyllithium, generated by the Shapiro reaction from 2-homoallylated cyclohexanone, gives a different regioisomer of 5: Chamberlin, A. R.; Bloom, S. H.; Cervini, L. A.; Fotsch, C. J. Am. Chem. Soc. 1988, 110, 4788-4796.
18. (a) Cheng, D.; Knox, K. R.; Cohen, T. J. Am. Chem. Soc. 2000, 122, 412-13.
19. (b) Cheng, D.; Zhu, S.; Yu, Z.; Cohen, T. J. Am. Chem. Soc. 2001, 123, 30-34.
20. The substrates 7 are prepared in one-flask reactions from commercial materials: Chen, F.; Mudryk, B.; Cohen, T. Tetrahedron 1999, 55, 3291-3304.
21. We suspect that the lithium oxyanions can participate in a nucleophilic fashion in metallo-ene cyclizations, which proceed via 6-center transition states, but prefer participation in an electrophilic fashion in alkyllithium cyclizations, which proceed via 4-center transition states. This concept will be further elaborated in a full article.
22. Cohen, T.; Gapinski, R. E.; Hutchins, R. R. J. Org. Chem 1979, 44, 3599-3601.
23. Lipshutz, B. H.; Sharma, S.; Dimock, S. H.; Behling, J. R. Synthesis 1992, 191-195.
24. Bakuzis, P.; Bakuuzis, M. L.; Fortes, C. C.; Santos, R. J. Org. Chem. 1976, 41, 2769-2770.
25. Aurell, M. J.; Gil, S.; Mestres, R., Parra, M.; Parra, L. Tetrahedron 1998, 54, 4357-4366.