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0001277227
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This proposal has been criticized based on negligible Lewis acidity of TMSC1 itself. See: Lipshutz, B. H.; Aue. D. H.; James, B. Tetrahedron Lett. 1996, 37, 8471. However, this does not exclude the discreet silylation of enones apparently depicted in ref 6.
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Frantz, D. E.; Singleton, D. A.; Snyder, J. P. J. Am. Chem. Soc. 1997, 119, 3383. A recent paper has concluded that the rate-limiting step is formation of the Cu(III) intermediate
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(see: Canisius, J.; Gerold, A.; Krause, N. Angew. Chem., Int. Ed. Engl. 1999, 38, 1644); however, this appears inconsistent with the observed isotope effects.
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84867104302
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Butylcopper is known to add to cyclohexenone at -78°C in the presense of TMSCI. See ref 5b
-
Butylcopper is known to add to cyclohexenone at -78°C in the presense of TMSCI. See ref 5b.
-
-
-
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29
-
-
33646329806
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note
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13C NMR and potential impurities. Small deviations from KIEs of 1.000 for these carbons will not affect the conclusions.
-
-
-
-
30
-
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33646315924
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This method was developed by S. R. Merrigan in this laboratory
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This method was developed by S. R. Merrigan in this laboratory.
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For a discussion of theoretical methodology for organocuprate structures, see: Nakamura, E.: Mori, S.; Nakamura, M.; Morokuma, K. J. Am. Chem. Soc. 1997, 119, 4887.
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0001615802
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Allowance for the equilibrium presence of the enone π complex as done here may decrease the discrepancy between experimental and calculated isotope effects in these reactions. See: Mori, S.; Nakamura, E. Chem. Eur. 7, 1999, 5, 1534-1543.
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0029798677
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See especially footnote 20. In addition, a recent paper by one of the original authors in ref 9 also states that with the use of a large excess of TMSCl, hydrolysis of the initially formed silyl enol ether occurs upon workup.
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Eriksson, M.; Johansson, A.; Nilsson, M.; Olsson, T. J. Am. Chem. Soc. 1996, 118, 10904. See especially footnote 20. In addition, a recent paper by one of the original authors in ref 9 also states that with the use of a large excess of TMSCl, hydrolysis of the initially formed silyl enol ether occurs upon workup.
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See: Bertz, S. H.; Chopra, A.; Eriksson, M.; Ogle, C. A.; Seagle, P. Chem. Eur. J. 1999, 5, 2680.
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0002668332
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(a) It is commonly assumed that equilibrium secondary hydrogen isotope effects are an upper bound for the kinetic isotope effect, though exceptions have been noted. See: Glad, S. S.; Jensen, F. J. Org. Chem. 1997, 62, 253.
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60
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33646298359
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Modeling of the secondary KIEs using equilibrium isotope effects is bolstered by the expectation that the endothermic silylation step should have a late transition state
-
(b) Modeling of the secondary KIEs using equilibrium isotope effects is bolstered by the expectation that the endothermic silylation step should have a late transition state.
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-
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61
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33646308858
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Molecular mechanics calculations (MM2) predict that having the tert-butyl group axial in 6-tert-butylcyclohexenone is disfavored by only 0.8 kcal/mol
-
Molecular mechanics calculations (MM2) predict that having the tert-butyl group axial in 6-tert-butylcyclohexenone is disfavored by only 0.8 kcal/mol.
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