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The barrier for the nitrogen inversion is expected to be higher in the eis isomer, and only one isomer, indeed, is seen. It is worth pointing out that the two invertomers of cis-configured aziridines should have different energies since the one that put the alkyl group cis to the phenyl rings is the less stable one
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The barrier for the nitrogen inversion is expected to be higher in the eis isomer, and only one isomer, indeed, is seen. It is worth pointing out that the two invertomers of cis-configured aziridines should have different energies since the one that put the alkyl group cis to the phenyl rings is the less stable one.
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8 on aziridine trans-la, it was possible to study the nitrogen inversion. Aziridine trans1a showed only one signal for the aziridine protons at 293 K; cooling down the sample to 195 K, a splitting into two lines for the above protons is observed testifying a slow nitrogen inversion. The reduced rate of inversion with respect to the NMR time scale makes the two aziridine protons diastereotopic and then distinguishable. No splitting was observed in the case of the corresponding cis-aziridine ring protons.
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8 on aziridine trans-la, it was possible to study the nitrogen inversion. Aziridine trans1a showed only one signal for the aziridine protons at 293 K; cooling down the sample to 195 K, a splitting into two lines for the above protons is observed testifying a slow nitrogen inversion. The reduced rate of inversion with respect to the NMR time scale makes the two aziridine protons diastereotopic and then distinguishable. No splitting was observed in the case of the corresponding cis-aziridine ring protons.
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A complex-induced proximity effect could be operative in the α-lithiation of aziridines trans-1a-d; see: Whisler, M. C.; MacNeil, S.; Snieckus, V.; Beak, P. Angew. Chem., Int. Ed. 2004, 43, 2206-2225.
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Some spectroscopical evidences from an NMR investigation on these lithiated intermediates are in agreement with this hypothesis and results will be reported in due course; see also: Hoffmann, R. W.; Ruhl, T.; Chemla, F.; Zahneisen, T. Liebigs Ann. Chem. 1992, 719-724.
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Some spectroscopical evidences from an NMR investigation on these lithiated intermediates are in agreement with this hypothesis and results will be reported in due course; see also: Hoffmann, R. W.; Ruhl, T.; Chemla, F.; Zahneisen, T. Liebigs Ann. Chem. 1992, 719-724.
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Moreover, we cannot rule out that an equilibrium between two isomeric lithiated intermediates could be present and that this could be differently shifted depending on the solvent
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Moreover, we cannot rule out that an equilibrium between two isomeric lithiated intermediates could be present and that this could be differently shifted depending on the solvent.
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Relative stereochemistry has been ascertained by NOESY 2D and ID experiments; see the Supporting Information for details.
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Relative stereochemistry has been ascertained by NOESY 2D and ID experiments; see the Supporting Information for details.
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In an attempt to demonstrate the intervening of a SET mechanism, bromomethylcyclopropane and 6-bromo-1-hexene were used as radical scavengers (see: (a) Gawley, R. E.; Low, E.; Zhang, Q.; Harris, R. J. Am. Chem. Soc. 2000, 122, 3344-3350.
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(b) Gawley, R. E.; Eddings, D. B.; Santiago, M.; Vicic, D. A. Org. Biomol. Chem. 2006, 4, 4285-4291) in the trapping reaction of trans-1a-Li in toluene and hexane as the solvents. A complex reaction mixture was obtained in both cases. Only a small amount of the desired alkylated products was observed from a GC-MS analysis.
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