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54249127403
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To ensure that all experiments were effected under identical conditions, two different sets of four samples each (one sample for each complex) for each solvent were irradiated at 15 cm of the light source in a irradiation chamber maintained to 25° by forced air circulation
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To ensure that all experiments were effected under identical conditions, two different sets of four samples each (one sample for each complex) for each solvent were irradiated at 15 cm of the light source in a irradiation chamber maintained to 25° by forced air circulation.
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28
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54249120851
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The effect of the solvent is, however, decisive in the carbonylation step as described in Figure 1. Coordinating solvents favor this step, while non-coordinating solvents hamper it. See ref 10 for a detailed discussion
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The effect of the solvent is, however, decisive in the carbonylation step as described in Figure 1. Coordinating solvents favor this step, while non-coordinating solvents hamper it. See ref 10 for a detailed discussion.
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30
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This enantio-discrimination observed in the conrotatory ring closure of the intermediate zwitterions in the formation of β-lactams is a case of asymmetric torquoselectivity. For a previous article in the asymmetric torquoselectivity of the Staudinger reaction, see: Cossío, F. P, Arrieta, A, Lecea, B, Ugalde, J. M. J. Am. Chem. Soc. 1994, 116, 2085
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This enantio-discrimination observed in the conrotatory ring closure of the intermediate zwitterions in the formation of β-lactams is a case of asymmetric torquoselectivity. For a previous article in the asymmetric torquoselectivity of the Staudinger reaction, see: Cossío, F. P.; Arrieta, A.; Lecea, B.; Ugalde, J. M. J. Am. Chem. Soc. 1994, 116, 2085.
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54249155570
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Interestingly, all the efforts made (including solvent effects and different combinations of functionals/basis sets) to locate the corresponding TS's associated with the attack of imine 9 to 6b, were fruitless.
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Interestingly, all the efforts made (including solvent effects and different combinations of functionals/basis sets) to locate the corresponding TS's associated with the attack of imine 9 to 6b, were fruitless.
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37
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54249153785
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This situation contrasts with the thermally generated chromium(0)-and tungsten(0)ketene imines by the reaction with isonitriles. In this case, the reactive species toward nucleophiles are the corresponding metallacyclopropanoneimines and the 1,2-chiomatropic rearrangement from these complexes to N-metal coordinated ketenimines is strongly exothermic
-
(a) This situation contrasts with the thermally generated chromium(0)-and tungsten(0)ketene imines by the reaction with isonitriles. In this case, the reactive species toward nucleophiles are the corresponding metallacyclopropanoneimines and the 1,2-chiomatropic rearrangement from these complexes to N-metal coordinated ketenimines is strongly exothermic,
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