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N2 displacement reactions.
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The term unactivated alkene is subject to a variety of interpretations. In the present context, we use this term to mean simple alkyl olefins, which traditionally have been among the least reactive alkenes in catalytic intermolecular amination reactions. Vinyl ethers, vinylarenes, dienes, and other alkenes containing electron-withdrawing or -donating groups or possessing the ability to chelate a metal center exhibit varying levels of activation. In addition, substrates that undergo intramolecular reaction should not be described as unactivated alkenes because of their intrinsic entropic activation relative to substrates that undergo intermolecular reaction.
-
The term "unactivated alkene" is subject to a variety of interpretations. In the present context, we use this term to mean simple alkyl olefins, which traditionally have been among the least reactive alkenes in catalytic intermolecular amination reactions. Vinyl ethers, vinylarenes, dienes, and other alkenes containing electron-withdrawing or -donating groups or possessing the ability to chelate a metal center exhibit varying levels of "activation". In addition, substrates that undergo intramolecular reaction should not be described as " unactivated" alkenes because of their intrinsic entropic "activation" relative to substrates that undergo intermolecular reaction.
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Gas-phase free energies of eqs 1 and 2 were obtained from density functional theory calculations (B3LYP/6-311++G**). Benchmarking studies comparing experimental and calculated energies suggest that the calculated values are within approximately 3 kcal/mol of the experimental data. See: Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Pople, J. A. J. Chem. Phys. 1997, 106, 1063-1079.
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Gas-phase free energies of eqs 1 and 2 were obtained from density functional theory calculations (B3LYP/6-311++G**). Benchmarking studies comparing experimental and calculated energies suggest that the calculated values are within approximately 3 kcal/mol of the experimental data. See: Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Pople, J. A. J. Chem. Phys. 1997, 106, 1063-1079.
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Formation of the Markovnikov enamine product in eq 2 is favored by 36.8 kcal/mol; formation of the imine tautomer is even more favorable, ΔG = -40.7 kcal/mol.
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Formation of the Markovnikov enamine product in eq 2 is favored by 36.8 kcal/mol; formation of the imine tautomer is even more favorable, ΔG = -40.7 kcal/mol.
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