Evidence for a concerted mechanism in a palladium trimethylenemethane cycloaddition

Journal of the American Chemical Society

Volumn 121, Issue 40, 1999, Pages 9313-9317

  Singleton, Daniel A ^a   Schulmeier, Brian E ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; AMIDE; CARBON 13; ESTER; METHANE; PALLADIUM COMPLEX;

ARTICLE; CHEMICAL REACTION; CYCLIZATION; DIASTEREOISOMER; REACTION ANALYSIS; STEREOSPECIFICITY;

EID: 0033552269     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9919229     Document Type: Article

References (35)

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9. Trost, B. M.; Renaut, P. J. Am. Chem. Soc. 1982, 104, 6668-72. Trost, B. M.; Lynch, J.; Renaut, P.; Steinman, D. H. J. Am. Chem. Soc. 1986, 108, 284-91. Paquette, L. A.; Sauer, D. R.; Cleary, D. G.; Kinsella, M. A.; Blackwell, C. M.; Anderson, L. G. J. Am. Chem. Soc. 1992, 114, 7375-87. Cossy, J.; Belotti, D.; Pete, J. P. Tetrahedron 1990, 46, 1859-70. Trost, B. M.; Acemoglu, M. Tetrahedron Lett. 1989, 30, 1495-8. Ishibashi, H.; Okano, M.; Tamaki, H.; Maruyama, K.; Yakura, T.; Ikeda, M. Chem. Commun. 1990, 1436-7.
10. Trost, B. M.; Renaut, P. J. Am. Chem. Soc. 1982, 104, 6668-72. Trost, B. M.; Lynch, J.; Renaut, P.; Steinman, D. H. J. Am. Chem. Soc. 1986, 108, 284-91. Paquette, L. A.; Sauer, D. R.; Cleary, D. G.; Kinsella, M. A.; Blackwell, C. M.; Anderson, L. G. J. Am. Chem. Soc. 1992, 114, 7375-87. Cossy, J.; Belotti, D.; Pete, J. P. Tetrahedron 1990, 46, 1859-70. Trost, B. M.; Acemoglu, M. Tetrahedron Lett. 1989, 30, 1495-8. Ishibashi, H.; Okano, M.; Tamaki, H.; Maruyama, K.; Yakura, T.; Ikeda, M. Chem. Commun. 1990, 1436-7.
11. Trost, B. M.; Renaut, P. J. Am. Chem. Soc. 1982, 104, 6668-72. Trost, B. M.; Lynch, J.; Renaut, P.; Steinman, D. H. J. Am. Chem. Soc. 1986, 108, 284-91. Paquette, L. A.; Sauer, D. R.; Cleary, D. G.; Kinsella, M. A.; Blackwell, C. M.; Anderson, L. G. J. Am. Chem. Soc. 1992, 114, 7375-87. Cossy, J.; Belotti, D.; Pete, J. P. Tetrahedron 1990, 46, 1859-70. Trost, B. M.; Acemoglu, M. Tetrahedron Lett. 1989, 30, 1495-8. Ishibashi, H.; Okano, M.; Tamaki, H.; Maruyama, K.; Yakura, T.; Ikeda, M. Chem. Commun. 1990, 1436-7.
12. Trost, B. M.; Renaut, P. J. Am. Chem. Soc. 1982, 104, 6668-72. Trost, B. M.; Lynch, J.; Renaut, P.; Steinman, D. H. J. Am. Chem. Soc. 1986, 108, 284-91. Paquette, L. A.; Sauer, D. R.; Cleary, D. G.; Kinsella, M. A.; Blackwell, C. M.; Anderson, L. G. J. Am. Chem. Soc. 1992, 114, 7375-87. Cossy, J.; Belotti, D.; Pete, J. P. Tetrahedron 1990, 46, 1859-70. Trost, B. M.; Acemoglu, M. Tetrahedron Lett. 1989, 30, 1495-8. Ishibashi, H.; Okano, M.; Tamaki, H.; Maruyama, K.; Yakura, T.; Ikeda, M. Chem. Commun. 1990, 1436-7.
13. Trost, B. M.; Renaut, P. J. Am. Chem. Soc. 1982, 104, 6668-72. Trost, B. M.; Lynch, J.; Renaut, P.; Steinman, D. H. J. Am. Chem. Soc. 1986, 108, 284-91. Paquette, L. A.; Sauer, D. R.; Cleary, D. G.; Kinsella, M. A.; Blackwell, C. M.; Anderson, L. G. J. Am. Chem. Soc. 1992, 114, 7375-87. Cossy, J.; Belotti, D.; Pete, J. P. Tetrahedron 1990, 46, 1859-70. Trost, B. M.; Acemoglu, M. Tetrahedron Lett. 1989, 30, 1495-8. Ishibashi, H.; Okano, M.; Tamaki, H.; Maruyama, K.; Yakura, T.; Ikeda, M. Chem. Commun. 1990, 1436-7.
14. Trost, B. M.; Chan, D. M. T. J. Am. Chem. Soc. 1980, 102, 6359-61.
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21. Bienaymé, H.; Longeau, A. Tetrahedron 1997, 28, 9637. Compound 5 may also be prepared by treating maleic anhydride with 2 equiv of diethylamine, isomerization of the resulting acid amide in refluxing toluene, and Fischer esterification.
22. Singleton, D. A.; Thomas, A. A. J. Am. Chem. Soc. 1995, 117, 9357-9358.
23. cis rate ratio and the potential cis-trans isomerization, we have not been able to conclude whether the formation of trans cycloadduct from maleates is the result of a nonstereospecific cycloaddition or prior isomerization of the maleate.
24. 13C peaks for the quaternary carbons in 11 were very narrow, and the standard deviations on their integrations were unusually large (up to 12%). For this reason, no meaningful KIE could be determined for the quaternary carbons.
25. 13C peaks for the diethylamide of 11 were not assigned, and the results for these carbons are shown arbitrarily in Figure 1.
26. After correction for ≈20% conversion, the actual KIEs would be ≈10% further from 1.000 than the values in Figure 1. This correction is small compared to the uncertainty in these values.
27. Due to broadening by exchange, the ethyl group carbons could not be integrated accurately. The methoxy group is subject to exchange with solvent under the reaction conditions, so no KIE could be determined for the methoxy carbon.
28. Singleton, D. A.; Szymanski, M. J. J. Am. Chem. Soc. 1999, 121, 9307-9312.
29. The KIEs discussed here are relative values for the absolute KIEs at reactive versus nonreactive methylene carbons of the Pd-TMM. The absolute KIEs for the nonreactive methylene carbons in each step are assumed to be near 1.000.
30. 14
31. 13C KIEs at the carbons associated with the less-formed bond at the transition state are near unity. Thus, the relatively strong but distant interaction of two carbons in a concerted cycloaddition need not result in a significant KIE, so the much weaker interaction in a stepwise cycloaddition seems very unlikely to produce a substantial KIE.
32. C < 1). See discussion in Yamataka, H.; Nagareda, K.; Takatsuka, T.; Ando, K.; Hanafusa, T.; Nagase, S. J. Am. Chem. Soc. 1993, 115, 8570. See also: Baddenbaum, W. E.; Shiner, V. J., Jr. In Isotope Effects on Enzyme- Catalyzed Reactions; Cleland, W. W., O'Leary, M. H., Northrop, D. B., Eds.; University Park Press: Baltimore, 1977; Chapter 1.
33. C < 1). See discussion in Yamataka, H.; Nagareda, K.; Takatsuka, T.; Ando, K.; Hanafusa, T.; Nagase, S. J. Am. Chem. Soc. 1993, 115, 8570. See also: Baddenbaum, W. E.; Shiner, V. J., Jr. In Isotope Effects on Enzyme-Catalyzed Reactions; Cleland, W. W., O'Leary, M. H., Northrop, D. B., Eds.; University Park Press: Baltimore, 1977; Chapter 1.
34. This discussion assumes that the equilibrium isotope effect at C4 for the first step is near 1.000. If the equilibrium isotope effect for the first step is in fact slightly inverse, as expected (see ref 23), the intrinsic isotope effects would have to be even larger.
35. DelMonte, A. J.; Haller, J.; Houk, K. N.; Sharpless, K. B.; Singleton, D. A.; Strassner, T.; Thomas, A. A. J. Am. Chem. Soc. 1997, 119, 9907-8.