Tandem cycloaddition chemistry of nitroalkenes: Probing the remarkable stereochemical influence of the Lewis acid

Journal of Organic Chemistry

Volumn 64, Issue 5, 1999, Pages 1610-1619

  Denmark, Scott E ^a   Seierstad, Mark ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHIRALITY; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS;

EID: 0033525699     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9820869     Document Type: Article

References (44)

1. Denmark, S. E.; Thorarensen, A. Chem. Rev. 1996, 96, 137.
2. Helmchen, G. In Stereoselective Synthesis, Methods of Organic Chemistry (Houben-Weyl); Edition E21a; Helmchen, G., Hoffmann, R., Mulzer, J., Schaumann, E., Eds.; Thieme: Stuttgart, 1995; Vol. 1, pp 1-74. This chapter uses the terms "simple" diastereoselectivity to describe the ratio of diastereomers with different relative configurations at the newly formed stereogenic centers, and "induced" diastereoselectivity to describe the ratio of diastereomers with the same relative configurations at the newly formed stereogenic centers (but, in this case, different relative to the preexisting stereogenic centers). We prefer the terms "relative" and "internal", respectively. Also, "external" diastereoselectivity (which is not relevant here) would refer to the absolute stereoselectivity imposed by an external chiral agent (such as a chiral Lewis acid).
3. Denmark, S. E.; Schnute, M. E.; Senanayake, C. B. W. J. Org. Chem. 1993, 58, 1859.
4. Denmark, S. E.; Senanayake, C. B. W.; Ho, G.-D. Tetrahedron 1990, 46, 4857.
5. (a) Denmark, S. E.; Herbert, B. J. Am. Chem. Soc. 1998, 120, 7357.
6. (b) Denmark, S. E.; Marcin, L. R. J. Org. Chem. 1997, 62, 1675.
7. Denmark, S. E.; Hurd, A. R.; Sacha, H. J. J. Org. Chem. 1997, 62, 1668.
8. Denmark, S. E.; Thorarensen, A.; Middleton, D. S. J. Am. Chem. Soc. 1998, 118, 8266.
9. Denmark, S. E.; Senanayake, C. B. W. J. Org. Chem. 1993, 58, 1853.
10. Santelli, M.; Pons, J.-M. Lewis Acids and Selectivity in Organic Synthesis; CRC Press: Boca Raton, 1996.
11. Denmark, S. E.; Dixon, J. A. J. Org. Chem. 1998, 63, 6178.
12. (a) Poll, T.; Helmchen, G.; Bauer, B. Tetrahedron Lett. 1984, 25, 2191.
13. (b) Suzuki, H.; Mochizuki, K.; Hattori, T.; Takahashi, N.; Tajima, O.; Takiguchi, T. Bull. Chem. Soc. Jpn. 1988, 61, 1999.
14. Waldmann, H. J. Org. Chem. 1988, 53, 6133.
15. Tietze, L. F.; Schneider, C.; Grote, A. Chem. Eur. J. 1996, 2, 139.
16. (e) Saito, T.; Suda, H.; Kawamura, M.; Nishimura, J.; Yamaya, A. Tetrahedron Lett. 1997, 38, 6035.
17. (a) Kiyooka, S.; Nakano, M.; Shiota, F.; Fujiyama, R. J. Org. Chem. 1989, 54, 5409.
18. (b) Yan, T.-H.; Tan, C.-W.; Lee, H.-C.; Lo, H.-C.; Huang, T.-Y. J. Am. Chem. Soc. 1993, 115, 2613.
19. Amoroso, R.; Cardillo, G.; Sabatino, P.; Tomasini, C.; Trerè, A. J. Org. Chem. 1993, 58, 5615.
20. Shimizu, M.; Kume, K.; Fujisawa, T. Tetrahedron Lett. 1995, 36, 5227.
21. Seebach, D.; Prelog, V. Angew. Chem., Int. Ed. Engl. 1982, 21, 654.
22. In the event that epimerization or isomerization need be considered, stereochemical designators may be used to explicitly describe the C(4a)-C(5) and C(5)-C(6) relationships.
23. 4 provided the cycloadduct 9 with only 25% conversion.
24. The enantiomeric ratio is simply the ratio of the major enantiomer to the minor, normalized to 1. The enantiomeric excess (% ee) can be calculated from the er by the equation % ee = (er - 1)/(er + 1) × 100. Because er is a direct measure of the relative rates of formation for two given products (and hence, the relative activation free energies leading to the respective transition structures) we believe it to be more useful than % ee when studying the stereochemical profile of a reaction. For a discussion of the relative merits of % ee and er, see Kagan, H. B. Recl. Trav. Chim. Pays-Bas 1995, 114, 203.
25. 2/MeOH (95/5). Detection wavelength: 220 nm. Retention times (min): (-)-10b, 3.18. (+)-10b, 3.56. (-)-10a, 4.04. (+)-10a, 4.66.
26. The er for 10b indicated the presence of a significant (∼4%) amount of (+)-10b in the product mixture. This could be derived from an l-(1,3-l) nitroso acetal 9d, which has never before been observed. Alternatively, isomerization of 8 to the Z isomer, followed by [4 + 2]/[3 + 2] cycloaddition could provide a u-(1,3-u) nitroso acetal which would be transformed to (+)-10b upon hydrogenolysis.
27. Pirkle, W. H.; Pochapsky, T. C. Chem. Rev. 1989, 89, 347.
28. Defining the topicity of the reactants at the other carbon would provide an explicit method to describe cycloadducts arising from epimerization or isomerization; however, this would create a nomenclature which is sensitive to the geometry of the alkene (whereas the cycloaddition is generally not) and which would be undefined in the case of monosubstituted dieneophiles.
29. Cardin, C. J.; Cardin, D. J.; Morton-Blake, D. A.; Parge, H. E.; Roy, A. J. Chem. Soc., Dalton Trans. 1987, 1641. A crystal structure of a mono-halide titanocene (with half of the molecules containing bromide, half with chloride) shows that the overall size and structure of the molecule is not significantly altered upon replacing chlorine with bromine, but rather governed primarily by the organic ligands.
30. (a) Avalos, M.; Babiano, R.; Cintas, P.; Higes, F. J.; Jiménez, J. L.; Palacios, J. C.; Silva, M. A. J. Org. Chem. 1996, 61, 1880.
31. (b) Tohda, Y.; Yamawaki, N.; Matsui, H.; Kawashima, T.; Ariga, M.; Mori, Y. Bull. Chem. Soc. Jpn. 1988, 61, 461.
32. Denmark, S. E.; Cramer, C. J.; Sternberg, J. A. Helv. Chim. Acta 1986, 69, 1971.
33. (a) Boyle, T. J.; Eilerts, N. W.; Heppert, J. A.; Takusagawa, F. Organometallics 1994, 13, 2218.
34. (b) Oppolzer, W.; Rodriguez, I.; Blagg, J.; Bernardinelli, G. Helv. Chim. Acta 1989, 72, 123.
35. Knight, C. T. G.; Merbach, A. E. Inorg. Chem. 1985, 24, 576.
36. Healy, M. D.; Ziller, J. W.; Barron, A. R. Organometallics 1991, 10, 597.
37. (a) Maria, P.-C.; Gal, J.-F. J. Phys. Chem. 1985, 89, 1296.
38. (b) Catalán, J.; Díaz, C.; López, V.; Pérez, P.; de Paz, J.-L. G.; Rodríguez, J. G. Liebigs Ann. 1996, 1785.
39. Gritzner, G. J. Mol. Liq. 1897, 73-74, 487.
40. (a) Electron-rich nitroalkenes (which might be thought to react slower as heterodienes in an inverse-electron demand Diels-Alder reaction) in fact undergo cycloaddition more rapidly than electron-deficient nitroalkenes, presumably because of more efficient coordination to the Lewis acid. Denmark, S. E.; Kesler, B. S.; Moon, Y.-C. J. Org. Chem. 1992, 57, 4912.
41. 4 to a nitroalkene has been examined with low-temperature NMR. Cramer, C. J. Ph.D. Thesis, University of Illinois, 1988. Ho, G.-D.; unpublished results from these laboratories.
42. Liu, J.; Niwayama, S.; You, Y.; Houk, K. N. J. Org. Chem. 1998, 63, 1064.
43. (a) Maruoka, K.; Nagahara, S.; Yamamoto, H. J. Am. Chem. Soc. 1990, 112, 6115.
44. (b) Saito, S.; Yamamoto, H. Chem. Commun. 1997, 1585.