Diels-alder cycloadditions of ethyl 2-carbomethoxyethenesulfinates with cyclopentadiene. Lewis acid enhancement and adduct identification with the assistance of competitive stereodifferentiating iodolactonization and iodosultinization reactions

Journal of Organic Chemistry

Volumn 64, Issue 22, 1999, Pages 8138-8143

  Lear, Yvonne ^a   Schwan, Adrian L ^a  

^a UNIVERSITY OF GUELPH   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPENTADIENE DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL MODIFICATION; CHEMICAL REACTION; CHEMICAL STRUCTURE; CRYSTAL STRUCTURE; CYCLIZATION; DIASTEREOISOMER; STRUCTURE ANALYSIS; X RAY CRYSTALLOGRAPHY;

EID: 0033615634     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo991082g     Document Type: Article

References (60)

1. Dell, C. P. J. Chem. Soc., Perkin Trans. 1 1998, 3873-3905.
2. (a) McClure, C. K.; Hansen, K. B. Tetrahedron Lett. 1996, 37, 2149-2152.
3. (b) Crowley, P. J.; Percy, J. M.; Stansfield, K. Tetrahedron Lett. 1996, 37, 8237-8240.
4. Byeon, C.-H.; Chen, C.-Y.; Ellis, D. A.; Hart, D. J.; Li, J. Synlett, 1998, 596-598.
5. Johnson, C. R.; Kadow, J. F. J. Org. Chem. 1987, 52, 1493-1500.
6. (e) Garcia Ruano, J. L.; Estaban Gamboa, A.; Martin Castro, A. M.; Rodriguez, J. H. J. Org. Chem. 1998, 63, 3324-3332.
7. (f) Sieburth, S. McN.; Lang, J. J. Org. Chem. 1999, 64, 1780-1781.
8. (a) De Lucchi, O.; Pasquato, L. Tetrahedron, 1988, 44, 6755-6794.
9. (b) Carreño, M. C. Chem. Rev. 1995, 95, 1717-1760.
10. Mikolajcyk, M.; Brabowicz, Kielbasinski, P. Chiral Sulfur Reagents: Applications in Asymmetric and Stereoselective Synthesis; CRC Press: Boca Raton, 1997; pp 158-169.
11. Westwell. A. D.; Rayner, C. M. In Organosulfur Chemistry: Synthetic and Stereochemical Aspects; Page, P., Ed.; Academic Press: New York, 1998; pp 192-211.
12. (a) Bovenschulte, E.; Metz, P.; Henkel, G. Angew. Chem., Int. Ed. Engl. 1989, 28, 202-203.
13. (b) Metz, P.; Fleischer, M. Synlett 1993, 399-400.
14. Metz, P.; Fleischer, M.; Fröhlich, R. Synlett 1992, 985-987.
15. Metz, P.; Fleischer, M.; Fröhlich, R. Tetrahedron 1995, 51, 711-732.
16. (e) Metz, P.; Cramer, E. Tetrahedron Lett. 1993, 34, 6371-6374.
17. (f) Metz, P.; Stölting, J.; Läge, M.; Krebs, B. Angew. Chem., Int. Ed. Engl. 1994, 33, 2195-2197.
18. (g) Meiners, U.; Cramer, E.; Fröhlich, R.; Wibbeling, B.; Metz, P. Eur. J. Org. Chem. 1998, 2073-2078.
19. Metz, P.; Seng, D.; Fröhlich, R.; Wibbeling, B. Synlett 1998, 741-742.
20. Brosius, A. D.; Overman, L. E.; Schwink, L. J. Am. Chem. Soc. 1999, 121, 700-709.
21. Galley, G.; Pätzel, M. J. Chem. Soc., Perkin Trans. 1 1996, 2297-2302.
22. Doye, S.; Hotopp, T.; Winterfeldt, E. Chem. Commun. 1997, 1491-1492.
23. (a) Lee, A. W. M.; Chan, W. H. Jiang, L. S.; Poon, K. W. Chem. Commun. 1997, 611-612.
24. (b) Chan, W. H.; Lee, A. W. M.; Jiang, L. S.; Mak, T. C. W. Tetrahedron: Asymmetry 1997, 8, 2501-2504.
25. Jiang, L. S.; Chan, W. H.; Lee, A. W. M. Tetrahedron 1999, 55, 2245-2262.
26. Klein, L. L.; Deeb, T. M. Tetrahedron Lett. 1985, 26, 3935-3938.
27. Chan, W. H.; Lee, A. W. M. Lee, K. M. J. Chem. Res., Synop. 1994, 138-139.
28. Schwan, A. L.; Snelgrove, J. L.; Kalin, M. L.; Froese, R. D. J.; Morokuma, K. Org. Lett. 1999, 1, 487-489.
29. (a) Hanson, G.; Kemp, D. S. J. Org. Chem. 1981, 46, 5441-5443.
30. (b) Dittmer, D. C.; Henion, R. S.; Takashina, N. J. Org. Chem. 1969, 34, 1310-1316.
31. Le Nocher, A.-M.; Metzner, P. Tetrahedron Lett. 1992, 33, 6151-6154.
32. Schwan, A. L.; Strickler, R. R.; Lear, Y.; Kalin, M. L.; Rietveld, T. E.; Xiang, T.-J.; Brillon, D. J. Org. Chem. 1998, 63, 7825-7832.
33. Oxner, O. In Correlation Analysis in Chemistry: Recent Advances; Chapman, N. B., Shorter, J., Eds.; Plenum Press: New York, 1978; Chapter 10.
34. See the Supporting Information for the improved experimental procedures.
35. The minor product in the cycloaddition mixture of dienophile 1 was assigned the structure of a cycloadduct on the basis of its GC retention time in relation to adducts 3 and on the basis of a GC-mass spectrum of the material. Its MS fragments were comparable to its isomeric cycloadducts. The sulflnyl configuration of 4 could not be finalized.
36. In Scheme 2, we have labeled the products of the cycloadditions with their proper stereochemistry. It should be noted that at the time of the reactions, the structures of the products was not known and they were only ascertained with the aid of X-ray analysis and iodocyclization experiments. We feel release of all of our information in this mode gives the smoothest presentation, although the data is not presented in the sequence consistent with discovery.
37. We adopt the nomenclature system based on configurational assignments as has been employed for sulfoxides; see ref 2a. When the S-OEt bond is positioned parallel to the bridgehead C-H bond on the same side of the molecule, the sulfinyl oxygen is either under the bicycle (syn) or is extended away from the molecule (anti).
38. ORTEP diagrams of compounds 3a and 8 and other pertinent X-ray data are part of the Supporting Information.
39. (a) Cha, C.-K.; Lee, S. J.; Tseng, W.-H. Tetrahedron Lett. 1997, 38, 2725-2728.
40. (b) Alonso, I.; Cid, M. B.; Carretero, J. C.; García Ruano, J. L.; Hoyos, M. A. Tetrahedron: Asymmetry 1991, 2, 1193-1207.
41. 1H NMR analysis of the crude mixture, but it could not be isolated. Analysis of that NMR suggested that the substrate had incorporated a methoxyethyl unit presumably by solvent (DME) intervention in the usual mode of cyclization.
42. (a) Kosugi, H.; Ku, J. Kato; M. J. Org. Chem. 1998, 63, 6939-6946.
43. (b) Alayrac, C.; Fromont, C.; Metzner, P.; Trong Anh, N. Angew. Chem., Int. Ed. Engl. 1997, 36, 371-374.
44. (a) Harpp, D. N.; Gleason, J. G. J. Org. Chem. 1971, 36, 1314-1316.
45. (b) Sharma, N. K.; de Reinach-Hirtzbach, F.; Durst, T.; Can. J. Chem. 1976, 54, 3012-3025.
46. Durst, T.; Huang, J. C.; Sharma, N. K.; Smith, D. J. H. Can. J. Chem. 1978, 56, 512-516.
47. The broad applicability of the syn-diaxial rule has been called into question in one instance. Ottenheijm and co-workers (Liskamp, R. M. J.; Zeegers, H. J. M.; Ottenheijm, H. C. J. J. Org. Chem. 1981, 46, 5408-5413) suggest that the rule is not applicable for five-membered sultines bearing pseudoaxial or pseudoequatorial substituents since those researchers did not observe any chemical shift differences of the appropriate hydrogens. We believe the rigid character of our polycycles satisfactorily allows the intended application of the syn-diaxial effect.
48. Additional, though less compelling, evidence in support of the relative assignments of 9a and 9b comes from the behavior of cyclic, epimeric sulfoxides. The sulfoxide isomer possessing the less hindered sulfinyl unit has been shown to elute slower on TLC, due to increased accessibility for association with the absorbent (Siegl, W. O.; Johnson, C. R. J. Org. Chem. 1970, 35, 3657-3663). We observe the same tendency with sultines 9a/b.
49. Experiments were run with 3 equiv of freshly distilled cyclopentadiene. Reaction temperature was room temperature unless otherwise noted; lower temperatures did not improve the selectivity of the Lewis acid mediated reactions. 1.2 equiv of Lewis acid were employed as lesser amounts were less effective.
50. Arai, Y.; Hayashi, Y, Yamamoto, M.; Takayama, H.; Koizumi, T. Chem Lett., 1987, 185-186.
51. Proust, S. M.; Ridley, D. D. Aust. J. Chem. 1984, 37, 1677-1688.
52. Maignan, C.; Guessous, A.; Rouessac F. Tetrahedron Lett. 1984, 25, 1727-1728.
53. Koizumi, T.; Arai, Y.; Takayama, H.; Kuriyama, K.; Shiro, M. Tetrahedron Lett. 1987, 28, 3689-3692.
54. Tou, J. S.; Reusch, W. J. Org. Chem. 1980, 45, 5012-5014.
55. Arai, Y.; Kuwayama, S.-I.; Takeuchi, Y.; Koizumi, T. Tetrahedron Lett. 1987, 28, 6205-6206.
56. By its design, the experiment requires that the addend reacting faster also gets consumed sooner. Thus even though equal concentrations of reactants are present at the outset, the course of the competition gives an advantage to the more sluggish reactant, as it will slowly gain a concentration advantage over the faster reactant. Therefore, the measured ratio of adducts represents the minimum rate difference between the two competitors.
57. 1H NMR. Diels-Alder reactions of 11 and 12 with cyclopentadiene had been performed independently and the major products from those reactions were obtained. Hence we were able to confidently identify and quantify all the peaks in the competition experiments. See the Supporting Information for data concerning the sulfoxide cycloadditions.
58. 2, 20 days), and the mixtures seem to be prone to decomposition. Our investigations with less substituted 1-alkenesulfinates are continuing.
59. Braverman, S.; Reisman, D. Tetrahedron Lett. 1977, 1753-1756.
60. Wu, H.-J.; Chao, C.-S.; Lin, C.-C. J. Org. Chem. 1998, 63, 7687-7693.