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26
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85038194402
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note
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Isolated Co(III)-salen complex 8-Br (see Experimental Section) was used for the study of solvent effect.
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-
-
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27
-
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85038199802
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note
-
It has been reported that the [2,3]Wittig rearrangement of both (E)- and (Z)-(2-alkenyloxy)acetic acid esters showed syn-selectivity (ref. 1a).
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-
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28
-
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85038198952
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-
note
-
To consider more about double diastereodifferentiation, we synthesized complex i and examined the reaction of 14 and (-)-menthyl α-diazoacetate using the complex as a catalyst. However, the reaction was sluggish, suggesting that the presence of the phenyl groups on the ethylenediamine moiety accelerated the desired reaction. The mechanism of this ligand acceleration is unclear at present. (equation presented)
-
-
-
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29
-
-
85038198832
-
-
note
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Configuration of the major diastereomer was tentatively assigned to be anti by the mechanical analogy with [2,3]sigmatropic rearrangement of the S-ylide derived from cinnamyl phenyl sulfide.
-
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-
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30
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1542503337
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0028263417
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35
-
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85038198796
-
-
note
-
These transition structures were searched and optimized by MOPAC Ver. 6.O. Each transition structure has only one imaginary frequency.
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-
-
-
36
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33751553846
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Transition structures of the sigmatropic rearrangement based on ab initia calculation were discussed: a) Wu, Y.-D.; Houk, K. N.; Marshall, J. A. J. Org. Chem. 1990, 55, 1421-1423.
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33845552223
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