Palladium-catalyzed intramolecular [3 + 2] cycloadditions of methylenecyclopropanes with alkenes: Diastereomeric methylenecyclopropanes exhibit complementary facial selectivity

Journal of the American Chemical Society

Volumn 118, Issue 43, 1996, Pages 10668-10669

  Lautens, Mark ^a   Ren, Yi ^a  

^a UNIVERSITY OF TORONTO   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

2 OXABICYCLO[3.3.0]OCTANE DERIVATIVE; BICYCLO[3.3.0]OCTANE DERIVATIVE; CYCLOPENTANE DERIVATIVE; FURAN DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0029796526     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja962148h     Document Type: Article

References (39)

1. For a review of transition metal mediated cycloadditions, see: (a) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49. For a review of [3 + 2] cycloadditions, see: (b) Chan, D. M. T. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 271. For reviews of [3 + 2] cycloaddition involving methylenecy-clopropane, see: (c) Binger, P.; Buch, H. M. Top. Curr. Chem. 1987, 135, 77. (d) Ohta, T.; Takaya, H. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 1185. (e) Dzhemilev, U. M.; Khusnutdinov, R. I.; Tolstikov, G. A. J. Organomet. Chem. 1991, 409, 15. (f) Binger, P.; Fox, D. In Methods of Organic Chemistry (Houben Weyl); Georg Thieme Verlag: Stuttgart, 1995; Vol. E 21C, Part D, 1.6.1.2.3, p 2997.
2. For a review of transition metal mediated cycloadditions, see: (a) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49. For a review of [3 + 2] cycloadditions, see: (b) Chan, D. M. T. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 271. For reviews of [3 + 2] cycloaddition involving methylenecy-clopropane, see: (c) Binger, P.; Buch, H. M. Top. Curr. Chem. 1987, 135, 77. (d) Ohta, T.; Takaya, H. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 1185. (e) Dzhemilev, U. M.; Khusnutdinov, R. I.; Tolstikov, G. A. J. Organomet. Chem. 1991, 409, 15. (f) Binger, P.; Fox, D. In Methods of Organic Chemistry (Houben Weyl); Georg Thieme Verlag: Stuttgart, 1995; Vol. E 21C, Part D, 1.6.1.2.3, p 2997.
3. For a review of transition metal mediated cycloadditions, see: (a) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49. For a review of [3 + 2] cycloadditions, see: (b) Chan, D. M. T. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 271. For reviews of [3 + 2] cycloaddition involving methylenecy-clopropane, see: (c) Binger, P.; Buch, H. M. Top. Curr. Chem. 1987, 135, 77. (d) Ohta, T.; Takaya, H. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 1185. (e) Dzhemilev, U. M.; Khusnutdinov, R. I.; Tolstikov, G. A. J. Organomet. Chem. 1991, 409, 15. (f) Binger, P.; Fox, D. In Methods of Organic Chemistry (Houben Weyl); Georg Thieme Verlag: Stuttgart, 1995; Vol. E 21C, Part D, 1.6.1.2.3, p 2997.
4. For a review of transition metal mediated cycloadditions, see: (a) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49. For a review of [3 + 2] cycloadditions, see: (b) Chan, D. M. T. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 271. For reviews of [3 + 2] cycloaddition involving methylenecy-clopropane, see: (c) Binger, P.; Buch, H. M. Top. Curr. Chem. 1987, 135, 77. (d) Ohta, T.; Takaya, H. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 1185. (e) Dzhemilev, U. M.; Khusnutdinov, R. I.; Tolstikov, G. A. J. Organomet. Chem. 1991, 409, 15. (f) Binger, P.; Fox, D. In Methods of Organic Chemistry (Houben Weyl); Georg Thieme Verlag: Stuttgart, 1995; Vol. E 21C, Part D, 1.6.1.2.3, p 2997.
5. For a review of transition metal mediated cycloadditions, see: (a) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49. For a review of [3 + 2] cycloadditions, see: (b) Chan, D. M. T. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 271. For reviews of [3 + 2] cycloaddition involving methylenecy-clopropane, see: (c) Binger, P.; Buch, H. M. Top. Curr. Chem. 1987, 135, 77. (d) Ohta, T.; Takaya, H. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 1185. (e) Dzhemilev, U. M.; Khusnutdinov, R. I.; Tolstikov, G. A. J. Organomet. Chem. 1991, 409, 15. (f) Binger, P.; Fox, D. In Methods of Organic Chemistry (Houben Weyl); Georg Thieme Verlag: Stuttgart, 1995; Vol. E 21C, Part D, 1.6.1.2.3, p 2997.
6. For a review of transition metal mediated cycloadditions, see: (a) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49. For a review of [3 + 2] cycloadditions, see: (b) Chan, D. M. T. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 271. For reviews of [3 + 2] cycloaddition involving methylenecy-clopropane, see: (c) Binger, P.; Buch, H. M. Top. Curr. Chem. 1987, 135, 77. (d) Ohta, T.; Takaya, H. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, p 1185. (e) Dzhemilev, U. M.; Khusnutdinov, R. I.; Tolstikov, G. A. J. Organomet. Chem. 1991, 409, 15. (f) Binger, P.; Fox, D. In Methods of Organic Chemistry (Houben Weyl); Georg Thieme Verlag: Stuttgart, 1995; Vol. E 21C, Part D, 1.6.1.2.3, p 2997.
7. (a) Lewis, R. T.; Motherwell, W. B.; Shipman, M. J. Chem. Soc., Chem. Commun. 1988, 948.
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13. (g) Yamago, S.; Nakamura, E. Tetrahedron 1989, 45, 3081.
14. (h) Corlay. H.; Motherwell, W. B.; Pennell, A. M. K.; Shipman, M.; Slawin, A. M. Z.; Williams, D. J. Tetrahedron 1996, 52, 4883.
15. (a) Lautens, M.; Ren, Y.; Delanghe, P. H. M. J. Am. Chem. Soc. 1994, 116, 8821.
16. (b) Lautens, M.; Ren, Y. J. Am. Chem. Soc. 1996, 118, 0000.
17. For example, in 2a the vinylic protons appear at 5.00 and 4.78 ppm, whereas in 5a they appear at 4.77 and 4.69 ppm and in 6a at 4.77 and 4.71 ppm. See Supporting Information for further details.
18. See Supporting Information.
19. Molecular sieves have been shown to improve some metal-catalyzed reactions. For examples, see: (a) Sharpless, K. B.; Michaelson, R. C. J. Am. Chem. Soc. 1973, 95, 6136. (b) Mihelich, E. D. Tetrahedron Lett. 1979, 20, 4729. Rossiter, B. E.; Verhoeven, T. R.; Sharpless, K. B. Tetrahedron Lett. 1979, 20, 4733.
20. Molecular sieves have been shown to improve some metal-catalyzed reactions. For examples, see: (a) Sharpless, K. B.; Michaelson, R. C. J. Am. Chem. Soc. 1973, 95, 6136. (b) Mihelich, E. D. Tetrahedron Lett. 1979, 20, 4729. Rossiter, B. E.; Verhoeven, T. R.; Sharpless, K. B. Tetrahedron Lett. 1979, 20, 4733.
21. Molecular sieves have been shown to improve some metal-catalyzed reactions. For examples, see: (a) Sharpless, K. B.; Michaelson, R. C. J. Am. Chem. Soc. 1973, 95, 6136. (b) Mihelich, E. D. Tetrahedron Lett. 1979, 20, 4729. (c) Rossiter, B. E.; Verhoeven, T. R.; Sharpless, K. B. Tetrahedron Lett. 1979, 20, 4733.
22. 2 in the Sm-catalyzed cyclopropanation provided the deuterated starting materials, see: ref 3. (a) Lautens, M.; Delanghe, P. H. M. J. Am. Chem. Soc. 1994, 116, 8526. (b) Lautens, M.; Ren, Y. J. Org. Chem. 1996, 61, 2210. For the preparation of dideuteriodiiodomethane, see: (c) Winstein, S.; Friedrich, E. C.; Baker, R.; Lin, Y. Tetrahedron Suppl. 1966, 8, 621.
23. 2 in the Sm-catalyzed cyclopropanation provided the deuterated starting materials, see: ref 3. (a) Lautens, M.; Delanghe, P. H. M. J. Am. Chem. Soc. 1994, 116, 8526. (b) Lautens, M.; Ren, Y. J. Org. Chem. 1996, 61, 2210. For the preparation of dideuteriodiiodomethane, see: (c) Winstein, S.; Friedrich, E. C.; Baker, R.; Lin, Y. Tetrahedron Suppl. 1966, 8, 621.
24. 2 in the Sm-catalyzed cyclopropanation provided the deuterated starting materials, see: ref 3. (a) Lautens, M.; Delanghe, P. H. M. J. Am. Chem. Soc. 1994, 116, 8526. (b) Lautens, M.; Ren, Y. J. Org. Chem. 1996, 61, 2210. For the preparation of dideuteriodiiodomethane, see: (c) Winstein, S.; Friedrich, E. C.; Baker, R.; Lin, Y. Tetrahedron Suppl. 1966, 8, 621.
25. 0 insertion into MCP, see: (a) Blomberg, M. R. A.; Siegbahn, P. E. M.; Bäckvall, J.-E. J. Am. Chem. Soc. 1987, 109, 4450 and references therein. The fate of the stereogenic carbon atom in a carbon-palladium complex upon reaction with an alkyne has been studied by Pfeffer. See: (b) Spencer J.; Pfeffer, M. Tetrahedron: Asymmetry 1995, 6, 419.
26. 0 insertion into MCP, see: (a) Blomberg, M. R. A.; Siegbahn, P. E. M.; Bäckvall, J.-E. J. Am. Chem. Soc. 1987, 109, 4450 and references therein. The fate of the stereogenic carbon atom in a carbon-palladium complex upon reaction with an alkyne has been studied by Pfeffer. See: (b) Spencer J.; Pfeffer, M. Tetrahedron: Asymmetry 1995, 6, 419.
27. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
28. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
29. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. (c) Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
30. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. (c) Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. (d) Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
31. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. (c) Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. (d) Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
32. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. (c) Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. (d) Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
33. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. (c) Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. (d) Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
34. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. (c) Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. (d) Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
35. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. (c) Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. (d) Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. (i) Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
36. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. (c) Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. (d) Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. (i) Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
37. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. (c) Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. (d) Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. (i) Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
38. trans-Bicyclo[3.3.0]octane is reported to be 6.1-6.4 kcal/mol less stable than its eis isomer. With the C-O bond length shorter than a C-C bond and the bond energy higher, the strain energy for the trans-fused cycloadduct can be very high. For examples of trans-bicyclo[3.3.0]octane, see: (a) Chang, S.; McNally, D.; Shary-Tehrany, S.; Mickey, M. J.; Boyd, R. H. J. Am. Chem. Soc. 1970, 92, 3109. (b) Allinger, N. L.; Tribble, M. T.; Miller, M. A.; Wertz, D. H. J. Am. Chem. Soc. 1971, 93, 1637. (c) Li, J.-H.; Allinger, N. L. J. Am. Chem. Soc. 1989, 111, 8566. (d) Linstead, R. P.; Meade, E. M. J. Chem. Soc. 1934, 935. (e) Funk, R. L.; Bolton, G. L.; Daggett, J. U.; Hansen, M. M. M.; Horcher, L. H. M. Tetrahedron 1985, 41, 3479. (f) Shibasaki, M. M. T.; Ikegami, S. J. Am. Chem. Soc. 1986, 108, 2090. (g) Rousset, C. J.; Swanson, D. R.; Lamaty, F.; Negishi, E. Tetrahedron Lett. 1989, 30, 5101. (h) Bailey, W. F.: Khanolkar, A. D. Tetrahedron Lett. 1990, 31, 5993. (i) Keese, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 344. (j) Hirschi, D.; Luef, W.; Gerber, P.; Keese, R. Helv. Chim. Acta 1992, 75, 1897. (k) Bourgin, D.; Buchel, R.; Gerber, P.; Keese, R. Tetrahedron Lett. 1994, 35, 3267. (l) Probert, G. D.; Whitby, R. J. Tetrahedron Lett. 1995, 36, 4113.
39. 2c,c,h The oxygen is part of the tether for each of the diastereomers we studied and cannot be solely responsible for the stereochemical outcome in the cycloaddition. Further studies will be reported in our full account of this work.