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See the Supporting Information for details
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Allylzinc reagents are likely not involved because such highly nucleophilic entities would not survive the reaction conditions, demonstrated previously to be acidic (see Ref. [2a])
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Allylzinc reagents are likely not involved because such highly nucleophilic entities would not survive the reaction conditions, demonstrated previously to be acidic (see Ref. [2a]).
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Catalyst screening indicated that aminophenol 1 b generally delivers somewhat higher enantioselectivity than 1 a
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Catalyst screening indicated that aminophenol 1 b generally delivers somewhat higher enantioselectivity than 1 a.
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71
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Initial isomerization of rac- 8 to (E)- and (Z)- 3 (prior to the first γ-addition to generate the chiral allylboron iii) is unlikely, as in that case, anti- 4 a would be formed with high diastereoselectivity. The stronger propensity of an aminophenol-based allylboron reagent to undergo a 1,3-borotropic shift is almost certainly due to its more Lewis acidic boron atom
-
Initial isomerization of rac- 8 to (E)- and (Z)- 3 (prior to the first γ-addition to generate the chiral allylboron iii) is unlikely, as in that case, anti- 4 a would be formed with high diastereoselectivity. The stronger propensity of an aminophenol-based allylboron reagent to undergo a 1,3-borotropic shift is almost certainly due to its more Lewis acidic boron atom.
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Attempts to observe (Z)- i through NMR spectroscopy were unsuccessful, as only a minute fraction of the aminophenol present is converted into the active catalyst
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Attempts to observe (Z)- i through NMR spectroscopy were unsuccessful, as only a minute fraction of the aminophenol present is converted into the active catalyst.
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73
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84961637348
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The chloro-substituted allylboron reagent was prepared by catalytic Z-selective cross-metathesis; see
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The chloro-substituted allylboron reagent was prepared by catalytic Z-selective cross-metathesis; see: M. J. Koh, T. T. Nguyen, H. Zhang, R. R. Schrock, A. H. Hoveyda, Nature 2016, DOI: 10.1038/nature17396.
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