Chiral bis(oxazoline)copper(II) complexes as lewis acid catalysts for the enantioselective Diels-Alder reaction

Journal of the American Chemical Society

Volumn 121, Issue 33, 1999, Pages 7559-7573

  Evans, David A ^a   Miller, Scott J ^a   Lectka, Thomas ^a   Von Matt, Peter ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COPPER DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL REACTION KINETICS; CHIRALITY; COMPLEX FORMATION; ENANTIOMER; STEREOCHEMISTRY;

EID: 0033603853     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991190k     Document Type: Article

References (108)

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21. N,N-Dialkyl acrylamides have a strong propensity for the s-cis conformation: Montaudo, G.; Librando, V.; Caccamese, S.; Maravigna, P. J. Am. Chem. Soc. 1973, 95, 6365-6370.
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24. For the catalysts illustrated in Figure 1, the absolute configurations of the ligand have been matched to the absolute configuration of the Diels-Alder adduct (eq 5).
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26. Fe(III): (a) Corey, E. J.; Imai, N.; Zhang, H.-Y. J. Am. Chem. Soc. 1991, 113, 728-729. Mg(II): (b) Corey, E. J.; Ishihara, K. Tetrahedron Lett. 1992, 33, 6807-6810.
27. Other bis(oxazoline)-metal complexes have been evaluated as catalysts. Mg (II): (a) Desimoni, G.; Faita, G.; Righetti, P. P. Tetrahedron Lett. 1996, 37, 3027-30. (b) Carbone, P.; Desimoni, G.; Faita, G.; Filippone, S.; Righetti, P. Tetrahedron 1998, 54, 6099-6110 and references therein. (c) Takacs, J. M.; Lawson, E. C.; Reno, M. J.; Youngman, M. A.; Quincy, D. A. Tetrahedron: Asymmetry 1997, 8, 3073-3078. (d) Takacs, J. M.; Quincy, D. A.; Shay, W.; Jones, B. E.; Ross, C. R. Tetrahedron: Asymmetry 1997, 8, 3079-3087. (e) Honda, Y.; Date, T.; Hiramatsu, H.; Yamauchi, M. Chem. Commun. 1997, 1411-1412. Zn(II): (f) Evans, D. A.; Kozlowski, M. C.; Tedrow, J. S. Tetrahedron Lett. 1996, 37, 7481-7484. For other Mg(II) complexes employed in Diels-Alder reactions, see: (g) Fujisawa, T.; Ichiyanagi, T.; Shimizu, M. Tetrahedron Lett. 1995, 36, 5031-5034. (h) Ichiyanagi, T.; Shimizu, M.; Fujisawa, T. J. Org. Chem. 1997, 62, 7937- 7941. (i) Ordoñez, M.; Guerrero de la Rosa, V.; Labastida, V.; Liera, J. M. Tetrahedron: Asymmetry 1996, 7, 2675-2686.
28. Other bis(oxazoline)-metal complexes have been evaluated as catalysts. Mg (II): (a) Desimoni, G.; Faita, G.; Righetti, P. P. Tetrahedron Lett. 1996, 37, 3027-30. (b) Carbone, P.; Desimoni, G.; Faita, G.; Filippone, S.; Righetti, P. Tetrahedron 1998, 54, 6099-6110 and references therein. (c) Takacs, J. M.; Lawson, E. C.; Reno, M. J.; Youngman, M. A.; Quincy, D. A. Tetrahedron: Asymmetry 1997, 8, 3073-3078. (d) Takacs, J. M.; Quincy, D. A.; Shay, W.; Jones, B. E.; Ross, C. R. Tetrahedron: Asymmetry 1997, 8, 3079-3087. (e) Honda, Y.; Date, T.; Hiramatsu, H.; Yamauchi, M. Chem. Commun. 1997, 1411-1412. Zn(II): (f) Evans, D. A.; Kozlowski, M. C.; Tedrow, J. S. Tetrahedron Lett. 1996, 37, 7481-7484. For other Mg(II) complexes employed in Diels-Alder reactions, see: (g) Fujisawa, T.; Ichiyanagi, T.; Shimizu, M. Tetrahedron Lett. 1995, 36, 5031-5034. (h) Ichiyanagi, T.; Shimizu, M.; Fujisawa, T. J. Org. Chem. 1997, 62, 7937- 7941. (i) Ordoñez, M.; Guerrero de la Rosa, V.; Labastida, V.; Liera, J. M. Tetrahedron: Asymmetry 1996, 7, 2675-2686.
29. Other bis(oxazoline)-metal complexes have been evaluated as catalysts. Mg (II): (a) Desimoni, G.; Faita, G.; Righetti, P. P. Tetrahedron Lett. 1996, 37, 3027-30. (b) Carbone, P.; Desimoni, G.; Faita, G.; Filippone, S.; Righetti, P. Tetrahedron 1998, 54, 6099-6110 and references therein. (c) Takacs, J. M.; Lawson, E. C.; Reno, M. J.; Youngman, M. A.; Quincy, D. A. Tetrahedron: Asymmetry 1997, 8, 3073-3078. (d) Takacs, J. M.; Quincy, D. A.; Shay, W.; Jones, B. E.; Ross, C. R. Tetrahedron: Asymmetry 1997, 8, 3079-3087. (e) Honda, Y.; Date, T.; Hiramatsu, H.; Yamauchi, M. Chem. Commun. 1997, 1411-1412. Zn(II): (f) Evans, D. A.; Kozlowski, M. C.; Tedrow, J. S. Tetrahedron Lett. 1996, 37, 7481-7484. For other Mg(II) complexes employed in Diels-Alder reactions, see: (g) Fujisawa, T.; Ichiyanagi, T.; Shimizu, M. Tetrahedron Lett. 1995, 36, 5031-5034. (h) Ichiyanagi, T.; Shimizu, M.; Fujisawa, T. J. Org. Chem. 1997, 62, 7937- 7941. (i) Ordoñez, M.; Guerrero de la Rosa, V.; Labastida, V.; Liera, J. M. Tetrahedron: Asymmetry 1996, 7, 2675-2686.
30. Other bis(oxazoline)-metal complexes have been evaluated as catalysts. Mg (II): (a) Desimoni, G.; Faita, G.; Righetti, P. P. Tetrahedron Lett. 1996, 37, 3027-30. (b) Carbone, P.; Desimoni, G.; Faita, G.; Filippone, S.; Righetti, P. Tetrahedron 1998, 54, 6099-6110 and references therein. (c) Takacs, J. M.; Lawson, E. C.; Reno, M. J.; Youngman, M. A.; Quincy, D. A. Tetrahedron: Asymmetry 1997, 8, 3073-3078. (d) Takacs, J. M.; Quincy, D. A.; Shay, W.; Jones, B. E.; Ross, C. R. Tetrahedron: Asymmetry 1997, 8, 3079-3087. (e) Honda, Y.; Date, T.; Hiramatsu, H.; Yamauchi, M. Chem. Commun. 1997, 1411-1412. Zn(II): (f) Evans, D. A.; Kozlowski, M. C.; Tedrow, J. S. Tetrahedron Lett. 1996, 37, 7481-7484. For other Mg(II) complexes employed in Diels-Alder reactions, see: (g) Fujisawa, T.; Ichiyanagi, T.; Shimizu, M. Tetrahedron Lett. 1995, 36, 5031-5034. (h) Ichiyanagi, T.; Shimizu, M.; Fujisawa, T. J. Org. Chem. 1997, 62, 7937- 7941. (i) Ordoñez, M.; Guerrero de la Rosa, V.; Labastida, V.; Liera, J. M. Tetrahedron: Asymmetry 1996, 7, 2675-2686.
31. Other bis(oxazoline)-metal complexes have been evaluated as catalysts. Mg (II): (a) Desimoni, G.; Faita, G.; Righetti, P. P. Tetrahedron Lett. 1996, 37, 3027-30. (b) Carbone, P.; Desimoni, G.; Faita, G.; Filippone, S.; Righetti, P. Tetrahedron 1998, 54, 6099-6110 and references therein. (c) Takacs, J. M.; Lawson, E. C.; Reno, M. J.; Youngman, M. A.; Quincy, D. A. Tetrahedron: Asymmetry 1997, 8, 3073-3078. (d) Takacs, J. M.; Quincy, D. A.; Shay, W.; Jones, B. E.; Ross, C. R. Tetrahedron: Asymmetry 1997, 8, 3079-3087. (e) Honda, Y.; Date, T.; Hiramatsu, H.; Yamauchi, M. Chem. Commun. 1997, 1411-1412. Zn(II): (f) Evans, D. A.; Kozlowski, M. C.; Tedrow, J. S. Tetrahedron Lett. 1996, 37, 7481-7484. For other Mg(II) complexes employed in Diels-Alder reactions, see: (g) Fujisawa, T.; Ichiyanagi, T.; Shimizu, M. Tetrahedron Lett. 1995, 36, 5031-5034. (h) Ichiyanagi, T.; Shimizu, M.; Fujisawa, T. J. Org. Chem. 1997, 62, 7937- 7941. (i) Ordoñez, M.; Guerrero de la Rosa, V.; Labastida, V.; Liera, J. M. Tetrahedron: Asymmetry 1996, 7, 2675-2686.
32. Other bis(oxazoline)-metal complexes have been evaluated as catalysts. Mg (II): (a) Desimoni, G.; Faita, G.; Righetti, P. P. Tetrahedron Lett. 1996, 37, 3027-30. (b) Carbone, P.; Desimoni, G.; Faita, G.; Filippone, S.; Righetti, P. Tetrahedron 1998, 54, 6099-6110 and references therein. (c) Takacs, J. M.; Lawson, E. C.; Reno, M. J.; Youngman, M. A.; Quincy, D. A. Tetrahedron: Asymmetry 1997, 8, 3073-3078. (d) Takacs, J. M.; Quincy, D. A.; Shay, W.; Jones, B. E.; Ross, C. R. Tetrahedron: Asymmetry 1997, 8, 3079-3087. (e) Honda, Y.; Date, T.; Hiramatsu, H.; Yamauchi, M. Chem. Commun. 1997, 1411-1412. Zn(II): (f) Evans, D. A.; Kozlowski, M. C.; Tedrow, J. S. Tetrahedron Lett. 1996, 37, 7481-7484. For other Mg(II) complexes employed in Diels-Alder reactions, see: (g) Fujisawa, T.; Ichiyanagi, T.; Shimizu, M. Tetrahedron Lett. 1995, 36, 5031-5034. (h) Ichiyanagi, T.; Shimizu, M.; Fujisawa, T. J. Org. Chem. 1997, 62, 7937- 7941. (i) Ordoñez, M.; Guerrero de la Rosa, V.; Labastida, V.; Liera, J. M. Tetrahedron: Asymmetry 1996, 7, 2675-2686.
33. Other bis(oxazoline)-metal complexes have been evaluated as catalysts. Mg (II): (a) Desimoni, G.; Faita, G.; Righetti, P. P. Tetrahedron Lett. 1996, 37, 3027-30. (b) Carbone, P.; Desimoni, G.; Faita, G.; Filippone, S.; Righetti, P. Tetrahedron 1998, 54, 6099-6110 and references therein. (c) Takacs, J. M.; Lawson, E. C.; Reno, M. J.; Youngman, M. A.; Quincy, D. A. Tetrahedron: Asymmetry 1997, 8, 3073-3078. (d) Takacs, J. M.; Quincy, D. A.; Shay, W.; Jones, B. E.; Ross, C. R. Tetrahedron: Asymmetry 1997, 8, 3079-3087. (e) Honda, Y.; Date, T.; Hiramatsu, H.; Yamauchi, M. Chem. Commun. 1997, 1411-1412. Zn(II): (f) Evans, D. A.; Kozlowski, M. C.; Tedrow, J. S. Tetrahedron Lett. 1996, 37, 7481-7484. For other Mg(II) complexes employed in Diels-Alder reactions, see: (g) Fujisawa, T.; Ichiyanagi, T.; Shimizu, M. Tetrahedron Lett. 1995, 36, 5031-5034. (h) Ichiyanagi, T.; Shimizu, M.; Fujisawa, T. J. Org. Chem. 1997, 62, 7937- 7941. (i) Ordoñez, M.; Guerrero de la Rosa, V.; Labastida, V.; Liera, J. M. Tetrahedron: Asymmetry 1996, 7, 2675-2686.
34. Other bis(oxazoline)-metal complexes have been evaluated as catalysts. Mg (II): (a) Desimoni, G.; Faita, G.; Righetti, P. P. Tetrahedron Lett. 1996, 37, 3027-30. (b) Carbone, P.; Desimoni, G.; Faita, G.; Filippone, S.; Righetti, P. Tetrahedron 1998, 54, 6099-6110 and references therein. (c) Takacs, J. M.; Lawson, E. C.; Reno, M. J.; Youngman, M. A.; Quincy, D. A. Tetrahedron: Asymmetry 1997, 8, 3073-3078. (d) Takacs, J. M.; Quincy, D. A.; Shay, W.; Jones, B. E.; Ross, C. R. Tetrahedron: Asymmetry 1997, 8, 3079-3087. (e) Honda, Y.; Date, T.; Hiramatsu, H.; Yamauchi, M. Chem. Commun. 1997, 1411-1412. Zn(II): (f) Evans, D. A.; Kozlowski, M. C.; Tedrow, J. S. Tetrahedron Lett. 1996, 37, 7481-7484. For other Mg(II) complexes employed in Diels-Alder reactions, see: (g) Fujisawa, T.; Ichiyanagi, T.; Shimizu, M. Tetrahedron Lett. 1995, 36, 5031-5034. (h) Ichiyanagi, T.; Shimizu, M.; Fujisawa, T. J. Org. Chem. 1997, 62, 7937-7941. (i) Ordoñez, M.; Guerrero de la Rosa, V.; Labastida, V.; Liera, J. M. Tetrahedron: Asymmetry 1996, 7, 2675-2686.
35. Other bis(oxazoline)-metal complexes have been evaluated as catalysts. Mg (II): (a) Desimoni, G.; Faita, G.; Righetti, P. P. Tetrahedron Lett. 1996, 37, 3027-30. (b) Carbone, P.; Desimoni, G.; Faita, G.; Filippone, S.; Righetti, P. Tetrahedron 1998, 54, 6099-6110 and references therein. (c) Takacs, J. M.; Lawson, E. C.; Reno, M. J.; Youngman, M. A.; Quincy, D. A. Tetrahedron: Asymmetry 1997, 8, 3073-3078. (d) Takacs, J. M.; Quincy, D. A.; Shay, W.; Jones, B. E.; Ross, C. R. Tetrahedron: Asymmetry 1997, 8, 3079-3087. (e) Honda, Y.; Date, T.; Hiramatsu, H.; Yamauchi, M. Chem. Commun. 1997, 1411-1412. Zn(II): (f) Evans, D. A.; Kozlowski, M. C.; Tedrow, J. S. Tetrahedron Lett. 1996, 37, 7481-7484. For other Mg(II) complexes employed in Diels-Alder reactions, see: (g) Fujisawa, T.; Ichiyanagi, T.; Shimizu, M. Tetrahedron Lett. 1995, 36, 5031-5034. (h) Ichiyanagi, T.; Shimizu, M.; Fujisawa, T. J. Org. Chem. 1997, 62, 7937- 7941. (i) Ordoñez, M.; Guerrero de la Rosa, V.; Labastida, V.; Liera, J. M. Tetrahedron: Asymmetry 1996, 7, 2675-2686.
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50. Seebach and others have provided additional contributions to this family of chiral titanium complexes: (a) Seebach, D.; Dahinden, R.; Marti, R. E.; Beck, A. K.; Planner, D. A.; Kuehnle, F. N. M. J. Org. Chem. 1995, 60, 1788-1799. (b) Haase, C.; Sarko, C. R.; DiMare, M. J. Org. Chem. 1995, 60, 1777-1787. (c) Chapuis, C.; Bauer, T.; Jezewski, A.; Jurczak, J. Pol. J. Chem. 1994, 65, 2323-31. (d) Gothelf, K. V.; Jørgensen, K. A. J. Org. Chem. 1995, 60, 6847-6851. (e) Reference 11a.
51. Seebach and others have provided additional contributions to this family of chiral titanium complexes: (a) Seebach, D.; Dahinden, R.; Marti, R. E.; Beck, A. K.; Planner, D. A.; Kuehnle, F. N. M. J. Org. Chem. 1995, 60, 1788-1799. (b) Haase, C.; Sarko, C. R.; DiMare, M. J. Org. Chem. 1995, 60, 1777-1787. (c) Chapuis, C.; Bauer, T.; Jezewski, A.; Jurczak, J. Pol. J. Chem. 1994, 65, 2323-31. (d) Gothelf, K. V.; Jørgensen, K. A. J. Org. Chem. 1995, 60, 6847-6851. (e) Reference 11a.
52. Seebach and others have provided additional contributions to this family of chiral titanium complexes: (a) Seebach, D.; Dahinden, R.; Marti, R. E.; Beck, A. K.; Planner, D. A.; Kuehnle, F. N. M. J. Org. Chem. 1995, 60, 1788-1799. (b) Haase, C.; Sarko, C. R.; DiMare, M. J. Org. Chem. 1995, 60, 1777-1787. (c) Chapuis, C.; Bauer, T.; Jezewski, A.; Jurczak, J. Pol. J. Chem. 1994, 65, 2323-31. (d) Gothelf, K. V.; Jørgensen, K. A. J. Org. Chem. 1995, 60, 6847-6851. (e) Reference 11a.
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73. (b) Ghosh, A. K.; Mathivanan, P.; Cappiello, J.; Krishnan, K. Tetrahedron: Asymmetry 1996, 7, 2165-2168.
74. (c) Ghosh, A. K.; Cho, H.; Cappiello, J. Tetrahedron: Asymmetry 1998, 9, 3687-3691.
75. Sagasser, I.; Helmchen, G. Tetrahedron Lett. 1998, 39, 261-264.
76. Brunel, J. M.; Del Campo, B.; Buono, G. Tetrahedron Lett. 1998, 39, 9663-9666.
77. 6c, 6d: (a) Reference 2a. (b) Woerpel, K. A. Ph.D. Thesis, Harvard University, 1992. (c) Evans, D. A.; Peterson, G. S.; Johnson, J. S.; Barnes, D. M.; Campos, K. R.; Woerpel, K. A. J. Org. Chem. 1998, 63, 4541- 4544. 6a: (d) Reference 13a. 6b: Prepared by Dr. Benjamin A. Anderson, Harvard University. Evans, D. A.; Anderson, B. A. Unpublished results.
78. 6c, 6d: (a) Reference 2a. (b) Woerpel, K. A. Ph.D. Thesis, Harvard University, 1992. (c) Evans, D. A.; Peterson, G. S.; Johnson, J. S.; Barnes, D. M.; Campos, K. R.; Woerpel, K. A. J. Org. Chem. 1998, 63, 4541-4544. 6a: (d) Reference 13a. 6b: Prepared by Dr. Benjamin A. Anderson, Harvard University. Evans, D. A.; Anderson, B. A. Unpublished results.
79. 6c, 6d: (a) Reference 2a. (b) Woerpel, K. A. Ph.D. Thesis, Harvard University, 1992. (c) Evans, D. A.; Peterson, G. S.; Johnson, J. S.; Barnes, D. M.; Campos, K. R.; Woerpel, K. A. J. Org. Chem. 1998, 63, 4541- 4544. 6a: (d) Reference 13a. 6b: Prepared by Dr. Benjamin A. Anderson, Harvard University. Evans, D. A.; Anderson, B. A. Unpublished results.
80. For a review of the coordination chemistry of Cu(II), see: Hathaway, B. J. In Comprehensive Coordination Chemistry; Wilkinson, G., Gillard, R. D., McClevarty, J. A., Eds.; Pergamon Press: Oxford, 1989; Vol. 5, pp 533-750.
81. Interestingly, in some cases the color of the catalyst was found to be thermochromic. For example, at room temperature, the catalyst solution was bright green, while at -78°C it had changed color to blue. Workup of the reaction involved simple dilution with 5 mL of 1:1 ethyl acetate/hexane, followed by filtration through a short plug of silica. This effectively removes all Cu salts, and the product can then be analyzed. See Experimental Section (Supporting Information) for details.
82. The syntheses of ligands 6a, 6c, and 6d may be found in the supplementary material of ref 2a.
83. 2, 53%; R = Ph, 92%, ref 14e.
84. See refs 13 and 14. The bias for the phenyl substituent with metals that coordinate in a tetrahedral geometry could result from both steric and electronic effects. Possible contributions from electronic effects have not yet been addressed.
85. Otto, S.; Bertoncin, F.; Engberts, J. B. F. N. J. Am. Chem. Soc. 1996, 118, 7702-7707.
86. Ag(I) salts have been used to generate cationic metal centers in other Diels- Alder catalysts. See ref 13b. See also: Hayashi, Y.; Rohde, J. J.; Corey, E. J. J. Am. Chem. Soc. 1996, 118, 5502-5503.
87. The optimized conditions include a substrate concentration of 0.3 M. To allow an accurate % conversion determination, the reactions illustrated graphically in Figure 2 were [5a] = 0.1 M.
88. While the study presented in Figure 3 indicates that the Diels-Alder reaction of acrylimide Sa with cyclopentadiene is complete after 1 h at -78°C, the reactions presented below were usually run for 4-8 h to ensure reproducibility of the results.
89. 2-catalyzed hetero Diels-Alder and ene reactions. Johannsen, M.; Jørgensen, K. A. Tetrahedron 1996 52, 7321-7328.
90. The structures of 9a and 9b have been reported. 9a: (a) Evans, D. A.; Olhava, E. J.; Johnson, J. S.; Janey, J. M. Angew. Chem., Int. Ed. Engl. 1998, 37, 3372-3375. 9b: (b) Reference 27c.
91. Evans, D. A.; Woerpel, K. A.; Scott, M. S. Angew. Chem., Int. Ed. Engl. 1992, 31, 430-432.
92. Four-coordinate Cu(II) complexes exhibit a strong tendency toward square-planar geometries. See ref 28.
93. Lawrence, G. A. Chem. Rev. 1986, 86, 17-33.
94. Kozlowski, M. C., unpublished results.
95. Engberts has recently reported water-enhanced enantioselectivity in a Diels-Alder reaction: Otto, S.; Boccaletti, G.; Engberts, J. J. Am. Chem. Soc. 1998, 120, 4238-4239. For other uses of aquo complexes in Diels-Alder reactions, see refs 21, 24c, and 38a.
96. Evans, D. A.; Burgey, C. S.; Paras, N. A.; Vojkovsky, T.; Tregay, S. T. J. Am. Chem. Soc. 1998, 120, 5824-5825.
97. These hetetocycles exhibit higher reactivity in acyl-transfer reactions. See, for example: Hsiao, C. N.; Liu, L.; Miller, M. J. J. Org. Chem. 1987, 52, 2201-2206.
98. (a) Damon, R. E.; Coppola, G. M. Tetrahedron Lett. 1990, 31, 2849-2852. (b) See also ref 8.
99. (-)-18 was subjected to a two-step sequence [(a) t-BuLi, (b) LAH] to afford the diol, which has been reported: Horton, D.; Machinami, T.; Takagi, Y. Carbohydr. Res. 1983, 121, 135-161.
100. For example, chiral norbornadienes would be useful starting materials for the synthesis of prostaglandins. Corey, E. J.; Shibasaki, M.; Nicolaou, K. C.; Malmsten, C. L.; Samuelson, B. Tetrahedron Lett. 1976, 17, 737-740.
101. For successful approaches to this problem, see: (a) Ishihara, K.; Kondo, S.; Kurihara, H.; Yamamoto, H.; Ohashi, S.; Inagaki, S. J. Org. Chem. 1997, 62, 3026-3027. (b) Corey, E. J.; Lee, T. W. Tetrahedron Lett. 1997, 38, 5755-5758.
102. For successful approaches to this problem, see: (a) Ishihara, K.; Kondo, S.; Kurihara, H.; Yamamoto, H.; Ohashi, S.; Inagaki, S. J. Org. Chem. 1997, 62, 3026-3027. (b) Corey, E. J.; Lee, T. W. Tetrahedron Lett. 1997, 38, 5755-5758.
103. Norris, W. P. J. Org. Chem. 1968, 33, 4540-4541.
104. Kobayashi has recently reported an interesting lanthanide-based Diels-Alder catalyst which turns over the sense of induction in the presence of potentially two-point binding competitive inhibitors: see ref 18b.
105. A discussion on inhibition by Laidler was found to be informative. Laidler, K. J. Chemical Kinetics; Harper and Row: New York, 1987.
106. A kinetic analysis has been done of a similar system: Chow, H.-F.; Mak, C. C. J. Org. Chem. 1997, 62, 5116-5127.
107. At the concentration of cyclopentadiene employed in the standard kinetics run at 0°C, dimerization was ascertained to be a maximum of 4% over a 24 h period.
108. in = [x∈]/[x-x∈][ln-x∈] (56) These reactions, employing Zn(II) complex 8a, were performed by Mr. Jason S. Tedrow, Harvard University.