Rhodium-Mediated Intramolecular C-H Insertion: Probing the Geometry of the Transition State

Journal of Organic Chemistry

Volumn 63, Issue 11, 1998, Pages 3717-3721

  Taber, Douglass F ^a   Malcolm, Scott C ^a  

^a UNIVERSITY OF DELAWARE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000438633     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9803434     Document Type: Article

References (36)

1. For general reviews of rhodium-mediated C - H insertions, see: (a) Taber D. F. Comprehensive Organic Synthesis; Pattenden, G., Ed.; Pergamon Press: Oxford, 1991; Vol. 3, pp 1045-1062. (b) Doyle, M. P. In Homogeneous Transition Metal Catalysts in Organic Synthesis; Moser, W. R., Slocum, D. W., Eds.; ACS Advanced Chemistry Series, No. 230; American Chemical Society: Washington, D.C., 1992; Chapter 30. Padwa, A.; Austin, D. J. Angew. Chem., Int. Ed. Engl. 1994, 53, 1797-1815. Ye, T.; McKervey, M. A. Chem. Rev. 1994, 94, 1091-1160.
2. For general reviews of rhodium-mediated C - H insertions, see: (a) Taber D. F. Comprehensive Organic Synthesis; Pattenden, G., Ed.; Pergamon Press: Oxford, 1991; Vol. 3, pp 1045-1062. (b) Doyle, M. P. In Homogeneous Transition Metal Catalysts in Organic Synthesis; Moser, W. R., Slocum, D. W., Eds.; ACS Advanced Chemistry Series, No. 230; American Chemical Society: Washington, D.C., 1992; Chapter 30. Padwa, A.; Austin, D. J. Angew. Chem., Int. Ed. Engl. 1994, 53, 1797-1815. Ye, T.; McKervey, M. A. Chem. Rev. 1994, 94, 1091-1160.
3. For general reviews of rhodium-mediated C - H insertions, see: (a) Taber D. F. Comprehensive Organic Synthesis; Pattenden, G., Ed.; Pergamon Press: Oxford, 1991; Vol. 3, pp 1045-1062. (b) Doyle, M. P. In Homogeneous Transition Metal Catalysts in Organic Synthesis; Moser, W. R., Slocum, D. W., Eds.; ACS Advanced Chemistry Series, No. 230; American Chemical Society: Washington, D.C., 1992; Chapter 30. Padwa, A.; Austin, D. J. Angew. Chem., Int. Ed. Engl. 1994, 53, 1797-1815. Ye, T.; McKervey, M. A. Chem. Rev. 1994, 94, 1091-1160.
4. For general reviews of rhodium-mediated C - H insertions, see: (a) Taber D. F. Comprehensive Organic Synthesis; Pattenden, G., Ed.; Pergamon Press: Oxford, 1991; Vol. 3, pp 1045-1062. (b) Doyle, M. P. In Homogeneous Transition Metal Catalysts in Organic Synthesis; Moser, W. R., Slocum, D. W., Eds.; ACS Advanced Chemistry Series, No. 230; American Chemical Society: Washington, D.C., 1992; Chapter 30. Padwa, A.; Austin, D. J. Angew. Chem., Int. Ed. Engl. 1994, 53, 1797-1815. Ye, T.; McKervey, M. A. Chem. Rev. 1994, 94, 1091-1160.
5. For more recent work on rhodium-mediated C - H insertions, see: (a) McCarthy, N.; McKervey, M. A.; Ye, T.; McCann, M.; Murphy, E.; Doyle, M. P. Tetrahedron Lett. 1992, 33, 5983-5986. (b) Doyle, M. P.; Dyatkin, A. B.; Roos, G. H. P.; Cañas, F.; Pierson, D. A.; Bastan, A, van; Müller, P.; Polleux, P. J. Am. Chem. Soc. 1994, 116, 4507-4508. Pirrung, M. C.; Morehead, A. T., Jr. J. Am. Chem. Soc. 1994, 116, 8991-9000. Ferns, L.; Haigh, D.; Moody, C. J. Tetrahedron Lett. 1996, 37, 107-110. (e) Taber, D. F.; You, K. K.; Rheingold, A. L. J. Am. Chem. Soc. 1996, 118, 547-556.
6. For more recent work on rhodium-mediated C - H insertions, see: (a) McCarthy, N.; McKervey, M. A.; Ye, T.; McCann, M.; Murphy, E.; Doyle, M. P. Tetrahedron Lett. 1992, 33, 5983-5986. (b) Doyle, M. P.; Dyatkin, A. B.; Roos, G. H. P.; Cañas, F.; Pierson, D. A.; Bastan, A, van; Müller, P.; Polleux, P. J. Am. Chem. Soc. 1994, 116, 4507-4508. Pirrung, M. C.; Morehead, A. T., Jr. J. Am. Chem. Soc. 1994, 116, 8991-9000. Ferns, L.; Haigh, D.; Moody, C. J. Tetrahedron Lett. 1996, 37, 107-110. (e) Taber, D. F.; You, K. K.; Rheingold, A. L. J. Am. Chem. Soc. 1996, 118, 547-556.
7. For more recent work on rhodium-mediated C - H insertions, see: (a) McCarthy, N.; McKervey, M. A.; Ye, T.; McCann, M.; Murphy, E.; Doyle, M. P. Tetrahedron Lett. 1992, 33, 5983-5986. (b) Doyle, M. P.; Dyatkin, A. B.; Roos, G. H. P.; Cañas, F.; Pierson, D. A.; Bastan, A, van; Müller, P.; Polleux, P. J. Am. Chem. Soc. 1994, 116, 4507-4508. Pirrung, M. C.; Morehead, A. T., Jr. J. Am. Chem. Soc. 1994, 116, 8991-9000. Ferns, L.; Haigh, D.; Moody, C. J. Tetrahedron Lett. 1996, 37, 107-110. (e) Taber, D. F.; You, K. K.; Rheingold, A. L. J. Am. Chem. Soc. 1996, 118, 547-556.
8. For more recent work on rhodium-mediated C - H insertions, see: (a) McCarthy, N.; McKervey, M. A.; Ye, T.; McCann, M.; Murphy, E.; Doyle, M. P. Tetrahedron Lett. 1992, 33, 5983-5986. (b) Doyle, M. P.; Dyatkin, A. B.; Roos, G. H. P.; Cañas, F.; Pierson, D. A.; Bastan, A, van; Müller, P.; Polleux, P. J. Am. Chem. Soc. 1994, 116, 4507-4508. Pirrung, M. C.; Morehead, A. T., Jr. J. Am. Chem. Soc. 1994, 116, 8991-9000. Ferns, L.; Haigh, D.; Moody, C. J. Tetrahedron Lett. 1996, 37, 107-110. (e) Taber, D. F.; You, K. K.; Rheingold, A. L. J. Am. Chem. Soc. 1996, 118, 547-556.
9. For more recent work on rhodium-mediated C - H insertions, see: (a) McCarthy, N.; McKervey, M. A.; Ye, T.; McCann, M.; Murphy, E.; Doyle, M. P. Tetrahedron Lett. 1992, 33, 5983-5986. (b) Doyle, M. P.; Dyatkin, A. B.; Roos, G. H. P.; Cañas, F.; Pierson, D. A.; Bastan, A, van; Müller, P.; Polleux, P. J. Am. Chem. Soc. 1994, 116, 4507-4508. Pirrung, M. C.; Morehead, A. T., Jr. J. Am. Chem. Soc. 1994, 116, 8991-9000. Ferns, L.; Haigh, D.; Moody, C. J. Tetrahedron Lett. 1996, 37, 107-110. (e) Taber, D. F.; You, K. K.; Rheingold, A. L. J. Am. Chem. Soc. 1996, 118, 547-556.
10. (a) For the cyclopropanation of α-diazo esters, see: Doyle, M. P. Chem. Rev. 1986, 86, 919-939. (b) For the cyclization of α-diazo ketones, see ref 1a.
11. (a) For the cyclopropanation of α-diazo esters, see: Doyle, M. P. Chem. Rev. 1986, 86, 919-939. (b) For the cyclization of α-diazo ketones, see ref 1a.
12. (a) For the cyclization of α-diazo-β-keto esters to form lactones, see: Doyle, M. P.; Westrum, L. J.; Wolthuis, W. N. E.; See, M. M.; Boone, W. P.; Bagheri, V.; Pearson, M. M. J. Am. Chem. Soc. 1993, 115, 958-964. For the cyclization of α-diazo-β-keto esters to form cyclopentanones, see: (b) Taber, D. F.; Raman, K. J. Am. Chem. Soc. 1983, 105, 5935-5937. Taber, D. F.; Raman, K.; Gaul, M. D. J. Org. Chem. 1987, 52, 28-34. For the cyclopropanation of α-diazo esters see: (d) Doyle, M. P. Recl. Trav. Chim. Pays-Bas 1991, 110, 305-316. (e) Davies, H. M. L.; Huby, N. J. S.; Cantrell, W. R., Jr.; Olive, J. L. J. Am. Chem. Soc. 1993, 115, 9468-9479. For the cyclization of α-diazo esters, see: (f) Taber, D. F.; You, K. K. J. Am. Chem. Soc. 1995, 117, 5757-5762. (g) Reference 2e. (h) For the cyclization of α-diazo ketones, see ref 1a.
13. (a) For the cyclization of α-diazo-β-keto esters to form lactones, see: Doyle, M. P.; Westrum, L. J.; Wolthuis, W. N. E.; See, M. M.; Boone, W. P.; Bagheri, V.; Pearson, M. M. J. Am. Chem. Soc. 1993, 115, 958-964. For the cyclization of α-diazo-β-keto esters to form cyclopentanones, see: (b) Taber, D. F.; Raman, K. J. Am. Chem. Soc. 1983, 105, 5935-5937. Taber, D. F.; Raman, K.; Gaul, M. D. J. Org. Chem. 1987, 52, 28-34. For the cyclopropanation of α-diazo esters see: (d) Doyle, M. P. Recl. Trav. Chim. Pays-Bas 1991, 110, 305-316. (e) Davies, H. M. L.; Huby, N. J. S.; Cantrell, W. R., Jr.; Olive, J. L. J. Am. Chem. Soc. 1993, 115, 9468-9479. For the cyclization of α-diazo esters, see: (f) Taber, D. F.; You, K. K. J. Am. Chem. Soc. 1995, 117, 5757-5762. (g) Reference 2e. (h) For the cyclization of α-diazo ketones, see ref 1a.
14. (a) For the cyclization of α-diazo-β-keto esters to form lactones, see: Doyle, M. P.; Westrum, L. J.; Wolthuis, W. N. E.; See, M. M.; Boone, W. P.; Bagheri, V.; Pearson, M. M. J. Am. Chem. Soc. 1993, 115, 958-964. For the cyclization of α-diazo-β-keto esters to form cyclopentanones, see: (b) Taber, D. F.; Raman, K. J. Am. Chem. Soc. 1983, 105, 5935-5937. Taber, D. F.; Raman, K.; Gaul, M. D. J. Org. Chem. 1987, 52, 28-34. For the cyclopropanation of α-diazo esters see: (d) Doyle, M. P. Recl. Trav. Chim. Pays-Bas 1991, 110, 305-316. (e) Davies, H. M. L.; Huby, N. J. S.; Cantrell, W. R., Jr.; Olive, J. L. J. Am. Chem. Soc. 1993, 115, 9468-9479. For the cyclization of α-diazo esters, see: (f) Taber, D. F.; You, K. K. J. Am. Chem. Soc. 1995, 117, 5757-5762. (g) Reference 2e. (h) For the cyclization of α-diazo ketones, see ref 1a.
15. (a) For the cyclization of α-diazo-β-keto esters to form lactones, see: Doyle, M. P.; Westrum, L. J.; Wolthuis, W. N. E.; See, M. M.; Boone, W. P.; Bagheri, V.; Pearson, M. M. J. Am. Chem. Soc. 1993, 115, 958-964. For the cyclization of α-diazo-β-keto esters to form cyclopentanones, see: (b) Taber, D. F.; Raman, K. J. Am. Chem. Soc. 1983, 105, 5935-5937. Taber, D. F.; Raman, K.; Gaul, M. D. J. Org. Chem. 1987, 52, 28-34. For the cyclopropanation of α-diazo esters see: (d) Doyle, M. P. Recl. Trav. Chim. Pays-Bas 1991, 110, 305-316. (e) Davies, H. M. L.; Huby, N. J. S.; Cantrell, W. R., Jr.; Olive, J. L. J. Am. Chem. Soc. 1993, 115, 9468-9479. For the cyclization of α-diazo esters, see: (f) Taber, D. F.; You, K. K. J. Am. Chem. Soc. 1995, 117, 5757-5762. (g) Reference 2e. (h) For the cyclization of α-diazo ketones, see ref 1a.
16. (a) For the cyclization of α-diazo-β-keto esters to form lactones, see: Doyle, M. P.; Westrum, L. J.; Wolthuis, W. N. E.; See, M. M.; Boone, W. P.; Bagheri, V.; Pearson, M. M. J. Am. Chem. Soc. 1993, 115, 958-964. For the cyclization of α-diazo-β-keto esters to form cyclopentanones, see: (b) Taber, D. F.; Raman, K. J. Am. Chem. Soc. 1983, 105, 5935-5937. Taber, D. F.; Raman, K.; Gaul, M. D. J. Org. Chem. 1987, 52, 28-34. For the cyclopropanation of α-diazo esters see: (d) Doyle, M. P. Recl. Trav. Chim. Pays-Bas 1991, 110, 305-316. (e) Davies, H. M. L.; Huby, N. J. S.; Cantrell, W. R., Jr.; Olive, J. L. J. Am. Chem. Soc. 1993, 115, 9468-9479. For the cyclization of α-diazo esters, see: (f) Taber, D. F.; You, K. K. J. Am. Chem. Soc. 1995, 117, 5757-5762. (g) Reference 2e. (h) For the cyclization of α-diazo ketones, see ref 1a.
17. (a) For the cyclization of α-diazo-β-keto esters to form lactones, see: Doyle, M. P.; Westrum, L. J.; Wolthuis, W. N. E.; See, M. M.; Boone, W. P.; Bagheri, V.; Pearson, M. M. J. Am. Chem. Soc. 1993, 115, 958-964. For the cyclization of α-diazo-β-keto esters to form cyclopentanones, see: (b) Taber, D. F.; Raman, K. J. Am. Chem. Soc. 1983, 105, 5935-5937. Taber, D. F.; Raman, K.; Gaul, M. D. J. Org. Chem. 1987, 52, 28-34. For the cyclopropanation of α-diazo esters see: (d) Doyle, M. P. Recl. Trav. Chim. Pays-Bas 1991, 110, 305-316. (e) Davies, H. M. L.; Huby, N. J. S.; Cantrell, W. R., Jr.; Olive, J. L. J. Am. Chem. Soc. 1993, 115, 9468-9479. For the cyclization of α-diazo esters, see: (f) Taber, D. F.; You, K. K. J. Am. Chem. Soc. 1995, 117, 5757-5762. (g) Reference 2e. (h) For the cyclization of α-diazo ketones, see ref 1a.
18. (a) For the cyclization of α-diazo-β-keto esters to form lactones, see: Doyle, M. P.; Westrum, L. J.; Wolthuis, W. N. E.; See, M. M.; Boone, W. P.; Bagheri, V.; Pearson, M. M. J. Am. Chem. Soc. 1993, 115, 958-964. For the cyclization of α-diazo-β-keto esters to form cyclopentanones, see: (b) Taber, D. F.; Raman, K. J. Am. Chem. Soc. 1983, 105, 5935-5937. Taber, D. F.; Raman, K.; Gaul, M. D. J. Org. Chem. 1987, 52, 28-34. For the cyclopropanation of α-diazo esters see: (d) Doyle, M. P. Recl. Trav. Chim. Pays-Bas 1991, 110, 305-316. (e) Davies, H. M. L.; Huby, N. J. S.; Cantrell, W. R., Jr.; Olive, J. L. J. Am. Chem. Soc. 1993, 115, 9468-9479. For the cyclization of α-diazo esters, see: (f) Taber, D. F.; You, K. K. J. Am. Chem. Soc. 1995, 117, 5757-5762. (g) Reference 2e. (h) For the cyclization of α-diazo ketones, see ref 1a.
19. Taber, D. F.; You, K.; Song, Y. J. Org. Chem. 1995, 60, 1093-1094.
20. For the preparation and use of Mosher esters, see: (a) Dale, J. A.; Dull, D. L.; Mosher, H. S. J. Org. Chem. 1969, 34, 2543-2549. (b) Balani, S. K.; Boyd, D. R.; Cassidy, E. S.; Greene, R. M. E.; McCombe, K. M.; Sharma, N. D.; Jennings, W. B. Tetrahedron Lett. 1981, 22, 3277-3280.
21. For the preparation and use of Mosher esters, see: (a) Dale, J. A.; Dull, D. L.; Mosher, H. S. J. Org. Chem. 1969, 34, 2543-2549. (b) Balani, S. K.; Boyd, D. R.; Cassidy, E. S.; Greene, R. M. E.; McCombe, K. M.; Sharma, N. D.; Jennings, W. B. Tetrahedron Lett. 1981, 22, 3277-3280.
22. For other methods of making enantiomerically enriched alcohol (R,R)-8, see, for example: (a) Suemune, H.; Okano, K.; Akita, H.; Sakai, K. Chem. Pharm. Bull. 1987, 35, 1741-1747. (b) Chen, M. Y.; Fang, J. M.; Tsai, Y. M.; Yeh, R. L. J. Chem. Soc., Chem. Commun. 1991, 1603-1604. Fang, C. L.; Suemune, H.; Sakai, K. J. Org. Chem. 1992, 57, 4300-4303.
23. For other methods of making enantiomerically enriched alcohol (R,R)-8, see, for example: (a) Suemune, H.; Okano, K.; Akita, H.; Sakai, K. Chem. Pharm. Bull. 1987, 35, 1741-1747. (b) Chen, M. Y.; Fang, J. M.; Tsai, Y. M.; Yeh, R. L. J. Chem. Soc., Chem. Commun. 1991, 1603-1604. Fang, C. L.; Suemune, H.; Sakai, K. J. Org. Chem. 1992, 57, 4300-4303.
24. For other methods of making enantiomerically enriched alcohol (R,R)-8, see, for example: (a) Suemune, H.; Okano, K.; Akita, H.; Sakai, K. Chem. Pharm. Bull. 1987, 35, 1741-1747. (b) Chen, M. Y.; Fang, J. M.; Tsai, Y. M.; Yeh, R. L. J. Chem. Soc., Chem. Commun. 1991, 1603-1604. Fang, C. L.; Suemune, H.; Sakai, K. J. Org. Chem. 1992, 57, 4300-4303.
25. Taber, D. F.; Saleh, S. A.; Korsmeyer, R. W. J. Org. Chem. 1980, 45, 4699-4702.
26. Corey, E. J.; Fuchs, P. L. J. Am. Chem. Soc. 1972, 94, 4014-4015.
27. Corey, E. J.; Posner, G. H. J. Am. Chem. Soc. 1968, 90, 5615-5616.
28. Taber, D. F.; Wang, Y.; Stachel, S. J. Tetrahedron Lett. 1993, 34, 6209-6210.
29. Taber, D. F.; Amedio, J. C., Jr.; Patel, Y. K. J. Org. Chem. 1985, 50, 3618-3619.
30. 1H NMR, and the amount of racemic alcohol ((R,R)-8 and (S,S)-8) was calculated and corrected for when determining the diastereomer ratio from the cyclization.
31. f (10% MTBE/petroleum ether) = 0.52. For leading references to the preparation of other rhodium carboxylates, see: (a) Felthouse, T. R. Prog. Inorg. Chem. 1982, 29, 73-166. (b) Jardine, F. H.; Sheridan, P. S. In Comprehensive Coordination Chemistry, IV; Wilkinson, G., Ed.; Pergamon Press: New York, 1987; pp 901-1096. Reference 1c and references within.
32. f (10% MTBE/petroleum ether) = 0.52. For leading references to the preparation of other rhodium carboxylates, see: (a) Felthouse, T. R. Prog. Inorg. Chem. 1982, 29, 73-166. (b) Jardine, F. H.; Sheridan, P. S. In Comprehensive Coordination Chemistry, IV; Wilkinson, G., Ed.; Pergamon Press: New York, 1987; pp 901-1096. Reference 1c and references within.
33. f (10% MTBE/petroleum ether) = 0.52. For leading references to the preparation of other rhodium carboxylates, see: (a) Felthouse, T. R. Prog. Inorg. Chem. 1982, 29, 73-166. (b) Jardine, F. H.; Sheridan, P. S. In Comprehensive Coordination Chemistry, IV; Wilkinson, G., Ed.; Pergamon Press: New York, 1987; pp 901-1096. Reference 1c and references within.
34. Taber, D. F.; Herr, R. J.; Pack, S. K.; Geremia, J. M. J. Org. Chem. 1996, 61, 2908-2910.
35. 2e We find that the minimum difference in the "transition state energies" necessary for high diastereoselectivity (>95%) following the Doyle model is about 1 kcal/ mol. In the case of the naphthylbornyl-derived ester 1c, the Doyle model predicts that the (R,R)-3 diastereomer is favored over any other >3 kcal/mol, indicating that (R,R)-3 should be formed as a single diastereomer. Experimentally, we find that the ratio of (R,R)-3 to (S,S)-3 is 8.4:1.0. Therefore, we conclude that the unconstrained Doyle model is not sufficiently predictive in the case of more complex esters such as 1c.
36. For general experimental procedures, see: Taber, D. F.; Meagley, R. P.; Doren, D. J. J. Org. Chem. 1996, 61, 5723-5728. Exceptions are noted.