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2] can be easily handled in air and weighed out on the benchtop, see
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2] did not provide any of the diene product in comparable yield
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We have yet to observe the intermediacy of the allene during the course of these reactions. Nonetheless, β-hydride eliminations from vinyl palladium(II) complexes to form allene intermediates have been proposed in other reactions although at much higher temperatures.
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An alternative explanation for the role of TMSOTf is the possibility that it promotes an unprecedented Z to E isomerization of the vinyl palladium(II) complex. In either case, however, the role of the carbonyl oxygen atom in attenuating reactivity remains the same
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An alternative explanation for the role of TMSOTf is the possibility that it promotes an unprecedented Z to E isomerization of the vinyl palladium(II) complex. In either case, however, the role of the carbonyl oxygen atom in attenuating reactivity remains the same.
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79959532523
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In an effort to study the β-hydride elimination and hydropalladation steps more closely reactions with deuterium-labelled enol triflates were performed, but were inconclusive because of deuterium scrambling in the diene πsystem as a result of equilibrating Pd-H(D) intermediates. See the Supporting Information for more details
-
In an effort to study the β-hydride elimination and hydropalladation steps more closely reactions with deuterium-labelled enol triflates were performed, but were inconclusive because of deuterium scrambling in the diene πsystem as a result of equilibrating Pd-H(D) intermediates. See the Supporting Information for more details.
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79959521832
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The base-mediated elimination of triflic acid from enol triflates to provide the corresponding alkynoate (or allenoate) could serve as a potential pathway for these reactions that bypasses the initial oxidative addition and subsequent β-hydride elimination from a vinyl palladium(II) complex. The success of reactions in the absence of base, however, is evidence against this alternative pathway
-
The base-mediated elimination of triflic acid from enol triflates to provide the corresponding alkynoate (or allenoate) could serve as a potential pathway for these reactions that bypasses the initial oxidative addition and subsequent β-hydride elimination from a vinyl palladium(II) complex. The success of reactions in the absence of base, however, is evidence against this alternative pathway.
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