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The isomers diast-4 seem to be the kinetically preferred compounds as we observed that at low conversion (ca. 10%) the ratio of diast-4/4 is approximately 2:1. After complete conversion the ratio became 1:1 and no change in this ratio was observed by stirring the reaction for a longer time (4 days). These results seem to indicate that the palladium species can not effect the complete isomerization of diast-4 into 4 in a reasonable time, even at higher palladium loadings (10 mol%).
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The isomers diast-4 seem to be the kinetically preferred compounds as we observed that at low conversion (ca. 10%) the ratio of diast-4/4 is approximately 2:1. After complete conversion the ratio became 1:1 and no change in this ratio was observed by stirring the reaction for a longer time (4 days). These results seem to indicate that the palladium species can not effect the complete isomerization of diast-4 into 4 in a reasonable time, even at higher palladium loadings (10 mol%).
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39
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60749088270
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CCDC 707907 (4d), 707906 (12 c) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data- request/cif.
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CCDC 707907 (4d), 707906 (12 c) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data- request/cif.
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The palladium(II)-catalyzed cycloisomerization of alkynol derivatives to give enol ethers or related compounds is a well established reaction. For references, see: A) K. Utimoto
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The palladium(II) complex may act as a Lewis acid catalyst that activates the imine. For an excellent account on σ- and π-electrophilic Lewis acids, see: A) Y. Yamamoto
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Alternatively, the formation of an o-quinonemethide intermediate from the imine 6 could also be considered, see: b R. S. Kumar, R. Nagarajan, P. T. Perumal, Synthesis 2004, 949-959.
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Alternatively, the formation of an o-quinonemethide intermediate from the imine 6 could also be considered, see: b) R. S. Kumar, R. Nagarajan, P. T. Perumal, Synthesis 2004, 949-959.
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The structural assignment of the chiral compounds 12g-i is based on extensive NMR spectroscopy investigations and is in agreement with the excellent work recently published by Fürstner and co-workers, see reference [7b]. Interestingly, the relative stereostructure of compounds 12g-i is the same as that found by these authors in the related revised structure of berkelic acid.
-
The structural assignment of the chiral compounds 12g-i is based on extensive NMR spectroscopy investigations and is in agreement with the excellent work recently published by Fürstner and co-workers, see reference [7b]. Interestingly, the relative stereostructure of compounds 12g-i is the same as that found by these authors in the related revised structure of berkelic acid.
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60749120021
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The acetal intermediate may evolve by formation of an o-quinonemethide intermediate, see reference [14].
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The acetal intermediate may evolve by formation of an o-quinonemethide intermediate, see reference [14].
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