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85009020583
-
-
note
-
-1). Though semiempirical calculation has a tendency to estimate the perpendicular and skew approach of ethylene slightly stable, the parallel approach of olefin was finally obtained as the most stable transition state (TS 15). Therefore, this tendency gave little effect on the conclusion.
-
-
-
-
54
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85009012891
-
-
note
-
1 as an axis (Fig. 14).
-
-
-
-
55
-
-
85009013830
-
-
note
-
-1), the phenyl groups attached to the ethylene bridge in the real experimental system should destabilize the structure 38 because of the steric repulsions. Therefore, it is plausible to adopt structure-11-type orientation of methoxy-carbonyl group as a basic orientation (Fig. 15).
-
-
-
-
56
-
-
85009020584
-
-
note
-
Nine rotational isomers were shown in Fig. 16
-
-
-
-
57
-
-
85009010136
-
-
note
-
To explain clearly, phenyl and acetyl groups were attached to the transition state 11 as a representative model, Any rotational isomers can be used for initial geometries and the same results were obtained.
-
-
-
-
58
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0345917271
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-
60
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85009019839
-
-
note
-
Direct analyses of the present cyclopropanation in real experimental system by the PM3(tm) method were very complicated, because the usual conformation search was not reliable. Too many unreasonable structures were obtained in such a large system and a slight difference in initial geometry often lead to different optimized structures. Therefore, it was required that the analyses started from a simple model system and developed into a real experimental system by step by step checking the validity of the afforded structures.
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-
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61
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0034603013
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Since the carbene carbon of the cobalt(II) carbene complex possessed a radical character, the initial bond formation preferentially occurred at the terminal carbon of styrene. Similar radical character was proposed in the salen-Mn catalyzed epoxidation by the density functional method, and it was indicated that the stereo-selectivity was dominated at the initial carbon-oxygen bond formation step. L. Cavallo and H. Jacobsen, Angew. Chem., Int. Ed. Engl., 39, 589 (2000).
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Cavallo, L.1
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62
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85009018526
-
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note
-
Unreasonable transition states were omitted.
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-
-
-
63
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85009010825
-
-
See the preceding paper
-
See the preceding paper.
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