Asymmetric organocatalysis of 4 + 3 cycloaddition reactions

Journal of the American Chemical Society

Volumn 125, Issue 8, 2003, Pages 2058-2059

  Harmata, Michael ^a   Ghosh, Sunil K ^a   Hong, Xuechuan ^a   Wacharasindhu, Sumrit ^a   Kirchhoefer, Patrick ^a  

^a UNIVERSITY OF MISSOURI   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; ALLYL COMPOUND; FURAN DERIVATIVE;

ARTICLE; ASYMMETRIC CATALYSIS; CHEMICAL REACTION; CHIRALITY; CONFORMATION; CYCLOADDITION; ENANTIOMER;

EID: 0037467053     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja029058z     Document Type: Article

References (23)

1. (a) Harmata, M. Acc. Chem. Res. 2001, 34, 595.
2. (b) Cha, J.; Oh, J. Curr. Org. Chem. 1998, 2, 217.
3. (c) Harmata, M. Heteroatom-Stabilized Allylic Cations in 4 + 3 Cycloaddition Reactions. Recent Research Developments in Organic Chemistry; Transworld Research Network: Trivandrum, 1997; Vol. 1, p 523.
4. (d) Rigby, J. H.; Pigge, F. C. Org. React. 1997, 51, 351-478.
5. For recent examples of asymmetric 4 + 3 cycloaddition reactions, see: (a) Kende, A. S.; Huang, H. Tetrahedron Lett. 1997, 38, 3353-3356. (b) Harmata, M.; Jones, D. E. J. Org. Chem. 1997, 62, 1578-1579. (c) Stark, C. B. W.; Eggert, U.; Hoffmann, H. M. R. Angew. Chem., Int. Ed. 1998, 37, 1266-1268. (d) Harmata, M.; Jones, D. E.; Kahraman, M.; Sharma, U.; Barnes, C. L. Tetrahedron Lett. 1999, 40, 1831-1834. (e) Myers, A. G.; Barbay, J. K. Org. Lett. 2001, 3, 425-428. (f) Xiong, H.; Hsung, R. P.; Berry, C. R.; Rameshkumar, C. J. Am. Chem. Soc. 2001, 123, 7174-7175. (g) Xiong, H.; Hsung, R. P.; Shen, L. Hahn, J. M. Tetrahedron Lett. 2002, 43, 4449-4453.
6. For recent examples of asymmetric 4 + 3 cycloaddition reactions, see: (a) Kende, A. S.; Huang, H. Tetrahedron Lett. 1997, 38, 3353-3356. (b) Harmata, M.; Jones, D. E. J. Org. Chem. 1997, 62, 1578-1579. (c) Stark, C. B. W.; Eggert, U.; Hoffmann, H. M. R. Angew. Chem., Int. Ed. 1998, 37, 1266-1268. (d) Harmata, M.; Jones, D. E.; Kahraman, M.; Sharma, U.; Barnes, C. L. Tetrahedron Lett. 1999, 40, 1831-1834. (e) Myers, A. G.; Barbay, J. K. Org. Lett. 2001, 3, 425-428. (f) Xiong, H.; Hsung, R. P.; Berry, C. R.; Rameshkumar, C. J. Am. Chem. Soc. 2001, 123, 7174-7175. (g) Xiong, H.; Hsung, R. P.; Shen, L. Hahn, J. M. Tetrahedron Lett. 2002, 43, 4449-4453.
7. For recent examples of asymmetric 4 + 3 cycloaddition reactions, see: (a) Kende, A. S.; Huang, H. Tetrahedron Lett. 1997, 38, 3353-3356. (b) Harmata, M.; Jones, D. E. J. Org. Chem. 1997, 62, 1578-1579. (c) Stark, C. B. W.; Eggert, U.; Hoffmann, H. M. R. Angew. Chem., Int. Ed. 1998, 37, 1266-1268. (d) Harmata, M.; Jones, D. E.; Kahraman, M.; Sharma, U.; Barnes, C. L. Tetrahedron Lett. 1999, 40, 1831-1834. (e) Myers, A. G.; Barbay, J. K. Org. Lett. 2001, 3, 425-428. (f) Xiong, H.; Hsung, R. P.; Berry, C. R.; Rameshkumar, C. J. Am. Chem. Soc. 2001, 123, 7174-7175. (g) Xiong, H.; Hsung, R. P.; Shen, L. Hahn, J. M. Tetrahedron Lett. 2002, 43, 4449-4453.
8. For recent examples of asymmetric 4 + 3 cycloaddition reactions, see: (a) Kende, A. S.; Huang, H. Tetrahedron Lett. 1997, 38, 3353-3356. (b) Harmata, M.; Jones, D. E. J. Org. Chem. 1997, 62, 1578-1579. (c) Stark, C. B. W.; Eggert, U.; Hoffmann, H. M. R. Angew. Chem., Int. Ed. 1998, 37, 1266-1268. (d) Harmata, M.; Jones, D. E.; Kahraman, M.; Sharma, U.; Barnes, C. L. Tetrahedron Lett. 1999, 40, 1831-1834. (e) Myers, A. G.; Barbay, J. K. Org. Lett. 2001, 3, 425-428. (f) Xiong, H.; Hsung, R. P.; Berry, C. R.; Rameshkumar, C. J. Am. Chem. Soc. 2001, 123, 7174-7175. (g) Xiong, H.; Hsung, R. P.; Shen, L. Hahn, J. M. Tetrahedron Lett. 2002, 43, 4449-4453.
9. For recent examples of asymmetric 4 + 3 cycloaddition reactions, see: (a) Kende, A. S.; Huang, H. Tetrahedron Lett. 1997, 38, 3353-3356. (b) Harmata, M.; Jones, D. E. J. Org. Chem. 1997, 62, 1578-1579. (c) Stark, C. B. W.; Eggert, U.; Hoffmann, H. M. R. Angew. Chem., Int. Ed. 1998, 37, 1266-1268. (d) Harmata, M.; Jones, D. E.; Kahraman, M.; Sharma, U.; Barnes, C. L. Tetrahedron Lett. 1999, 40, 1831-1834. (e) Myers, A. G.; Barbay, J. K. Org. Lett. 2001, 3, 425-428. (f) Xiong, H.; Hsung, R. P.; Berry, C. R.; Rameshkumar, C. J. Am. Chem. Soc. 2001, 123, 7174-7175. (g) Xiong, H.; Hsung, R. P.; Shen, L. Hahn, J. M. Tetrahedron Lett. 2002, 43, 4449-4453.
10. For recent examples of asymmetric 4 + 3 cycloaddition reactions, see: (a) Kende, A. S.; Huang, H. Tetrahedron Lett. 1997, 38, 3353-3356. (b) Harmata, M.; Jones, D. E. J. Org. Chem. 1997, 62, 1578-1579. (c) Stark, C. B. W.; Eggert, U.; Hoffmann, H. M. R. Angew. Chem., Int. Ed. 1998, 37, 1266-1268. (d) Harmata, M.; Jones, D. E.; Kahraman, M.; Sharma, U.; Barnes, C. L. Tetrahedron Lett. 1999, 40, 1831-1834. (e) Myers, A. G.; Barbay, J. K. Org. Lett. 2001, 3, 425-428. (f) Xiong, H.; Hsung, R. P.; Berry, C. R.; Rameshkumar, C. J. Am. Chem. Soc. 2001, 123, 7174-7175. (g) Xiong, H.; Hsung, R. P.; Shen, L. Hahn, J. M. Tetrahedron Lett. 2002, 43, 4449-4453.
11. For recent examples of asymmetric 4 + 3 cycloaddition reactions, see: (a) Kende, A. S.; Huang, H. Tetrahedron Lett. 1997, 38, 3353-3356. (b) Harmata, M.; Jones, D. E. J. Org. Chem. 1997, 62, 1578-1579. (c) Stark, C. B. W.; Eggert, U.; Hoffmann, H. M. R. Angew. Chem., Int. Ed. 1998, 37, 1266-1268. (d) Harmata, M.; Jones, D. E.; Kahraman, M.; Sharma, U.; Barnes, C. L. Tetrahedron Lett. 1999, 40, 1831-1834. (e) Myers, A. G.; Barbay, J. K. Org. Lett. 2001, 3, 425-428. (f) Xiong, H.; Hsung, R. P.; Berry, C. R.; Rameshkumar, C. J. Am. Chem. Soc. 2001, 123, 7174-7175. (g) Xiong, H.; Hsung, R. P.; Shen, L. Hahn, J. M. Tetrahedron Lett. 2002, 43, 4449-4453.
12. (a) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 7894-7895.
13. (b) Northrop, A. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 2458-2460.
14. (c) Austin, J. F.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 1172-1173.
15. (d) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371.
16. The pentadienal 1 has been used in 4 + 3 cycloaddition reactions previously, see: Ohno, M.; Mori, K.; Hattori, T.; Eguchi, S. J. Org. Chem. 1990, 55, 6086-6091.
17. The assignment was made on the basis of the results of Eguchi and co-workers. See ref 4.
18. We do not know the absolute configuration of the major enantiomer for this or any other cycloaddition adduct reported here.
19. Parrill, A. L.; Dolata, D. P. THEOCHEM 1996, 370, 187.
20. The stereochemistry of 20 was established by a NOESY experiment.
21. The assignment of relative stereochemistry was based on chemical shift data of the 4-methyl group and aldehyde proton in 21. NOESY also supported the assignment. Details are given in the Supporting Information. See ref4 and (a) Montaña, A. M.; Grima, P. M.; Garcia, F. Magn. Reson. Chem. 1999, 37, 507. (b) Montaña, A. M.; Ribes, S.; Grima, P. M.; Garcia, F. Magn. Reson. Chem. 1998, 36, 174.
22. The assignment of relative stereochemistry was based on chemical shift data of the 4-methyl group and aldehyde proton in 21. NOESY also supported the assignment. Details are given in the Supporting Information. See ref4 and (a) Montaña, A. M.; Grima, P. M.; Garcia, F. Magn. Reson. Chem. 1999, 37, 507. (b) Montaña, A. M.; Ribes, S.; Grima, P. M.; Garcia, F. Magn. Reson. Chem. 1998, 36, 174.
23. However, the reaction of 20 with cyclopentadiene produced cycloadducts with enantiomeric excesses in the 50-60% range. Details will be reported later.