First Enantioselective Catalytic Diels-Alder Reaction of Dienes and Acetylenic Aldehydes: Experimental and Theoretical Evidence for the Predominance of Exo-Transition Structure

Journal of Organic Chemistry

Volumn 62, Issue 10, 1997, Pages 3026-3027

  Ishihara, Kazuaki ^a   Kondo, Shoichi ^a   Kurihara, Hideki ^a   Yamamoto, Hisashi ^a   Ohashi, Shigenori ^b   Inagaki, Satoshi ^b  

^a NAGOYA UNIVERSITY   (Japan)

^b GIFU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001621204     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970171v     Document Type: Article

References (25)

1. (a) Furuta, K.; Shimizu, S.; Miwa, Y.; Yamamoto, H. J. Org. Chem. 1989, 54, 1481.
2. (b) Ishihara, K.; Qingzhi, G.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 10412.
3. (c) Ishihara, K.; Qingzhi, G.; Yamamoto, H. J. Org. Chem. 1993, 58, 6917.
4. (d) Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116, 1561.
5. (e) Ishihara, K.; Kurihara, H.; Yamamoto, H. J. Am. Chem. Soc. 1996, 118, 3049.
6. For a recent review, see: Ishihara, K.; Yamamoto, H. In Advances in Catalytic Processes; Doyle, M. P., Ed.; JAI Press: London, 1995; Vol. 1, pp 29-59.
7. Hayashi, Y.; Rhode, J. J.; Corey, E. J. J. Am. Chem. Soc. 1996, 118, 5502 and references cited therein.
8. For a comprehensive review, see: Fucks, R.; Viehe, H. G. In Chemistry of Acetylenes; Viehe, H. G., Ed.; Marcel Dekker: New York, 1969; pp 425-595.
9. We previously reported the Diels-Alder reaction of cyclopentadiene and methyl propiolate catalyzed by a chiral organoaluminum reagent, giving the cycloadduct in 55% ee. Maruoka, K.; Concepcion, A. B.; Yamamoto, H. Bull. Chem. Soc. Jpn. 1992, 65, 3501.
10. In the reaction of propynal and cyclopentadiene, the desired reaction and the over reaction of 4 and cyclopentadiene proceed competitively.
11. Corey, E. J.; Shibasaki, M.; Nicolaou, K. C.; Malmsten, C. L.; Samuelsson, B. Tetrahedron Lett. 1976, 737.
12. (a) Sato, K.; Miyamoto, O.; Inoue, S.; Honda, K. Chem. Lett. 1981, 1183.
13. (b) Monti, H.; Corriol, C.; Bertrand, M. Tetrahedron Lett. 1982, 23, 947 and 5539.
14. For determination of the absolute configuration of aldol adducts, see the Supporting Information.
15. Steric shielding of the si-face of aldehydes is consistent with other previously reported enantioselective reactions catalyzed by 1; see: Ishihara, K.; Maruyama, T.; Mouri, M.; Gao, Q.; Furuta, K.; Yamamoto, H. Bull. Chem. Soc. Jpn. 1993, 66, 3483. Ishihara, K.; Mouri, M.; Gao, Q.; Maruyama, T.; Furuta, K.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 11490. Gao, Q.; Ishihara, K.; Maruyama, T.; Mouri, M.; Yamamoto, H. Tetrahedron 1994, 50, 979.
16. Steric shielding of the si-face of aldehydes is consistent with other previously reported enantioselective reactions catalyzed by 1; see: Ishihara, K.; Maruyama, T.; Mouri, M.; Gao, Q.; Furuta, K.; Yamamoto, H. Bull. Chem. Soc. Jpn. 1993, 66, 3483. Ishihara, K.; Mouri, M.; Gao, Q.; Maruyama, T.; Furuta, K.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 11490. Gao, Q.; Ishihara, K.; Maruyama, T.; Mouri, M.; Yamamoto, H. Tetrahedron 1994, 50, 979.
17. Steric shielding of the si-face of aldehydes is consistent with other previously reported enantioselective reactions catalyzed by 1; see: Ishihara, K.; Maruyama, T.; Mouri, M.; Gao, Q.; Furuta, K.; Yamamoto, H. Bull. Chem. Soc. Jpn. 1993, 66, 3483. Ishihara, K.; Mouri, M.; Gao, Q.; Maruyama, T.; Furuta, K.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 11490. Gao, Q.; Ishihara, K.; Maruyama, T.; Mouri, M.; Yamamoto, H. Tetrahedron 1994, 50, 979.
18. For theoretical studies, see: (a) Fleming, I. Frontier Orbitals and Organic Chemical reactions; Wiley: New York, 1976; Chapter 4. (b) Birney, D. M.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 4127. (c) Yamabe, S.; Dai, T.; Minato, T. J. Am. Chem. Soc. 1995, 117, 10994 and references cited therein.
19. For theoretical studies, see: (a) Fleming, I. Frontier Orbitals and Organic Chemical reactions; Wiley: New York, 1976; Chapter 4. (b) Birney, D. M.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 4127. (c) Yamabe, S.; Dai, T.; Minato, T. J. Am. Chem. Soc. 1995, 117, 10994 and references cited therein.
20. For theoretical studies, see: (a) Fleming, I. Frontier Orbitals and Organic Chemical reactions; Wiley: New York, 1976; Chapter 4. (b) Birney, D. M.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 4127. (c) Yamabe, S.; Dai, T.; Minato, T. J. Am. Chem. Soc. 1995, 117, 10994 and references cited therein.
21. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T. A.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrewsky, V. G.; Ortiz, J. W.; 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 94, Gaussian, Inc.: Pittsburgh, PA, 1995.
22. As a control experiment, our calculations provided the expected endo-TS for the reaction of acrolein with cyclopentadiene as is observed experimentally. For further particulars, see the Supporting Information.
23. The frontier molecular-orbital theory explains exo selectivity in terms of the secondary antibonding interaction between the lobes on C-2 of cyclopentadiene and carbonyl oxygen of propynal in endo-TS. Chemical equations presented
24. 2=3.342, 3.511 Å TS (d=distances shown by dotted lines)
25. H.K. acknowledges a JSPS Fellowship for Japanese Junior Scientists. We thank Mr. Manabu Kubota for his helpful discussions.