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This fast isomerization could be due to the benzylic hydrogen, whose acidity, by favoring a fast isomerization of the terminal isomer, inhibits further arylation into the double-arylated product.
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65
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0242295451
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note
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a values of acetate and pivalate anions in TBAB cannot be the same as those measured in water. This would not be surprising, since in these solvents the anions, being poorly solvated, should be both good nucleophiles for palladium and stronger bases.
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66
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0001589134
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Evidence for ligation of acetate ion to Pd(0) and Pd(II) intermediates was reported: Amatore, C.; Carré, E.; Jutand, A.; M'Barki, M. A.; Meyer, G. Organometallics 1995, 14, 5605-5614. Our data, however, cannot discriminate whether the PdH neutralization by acetate is an intermolecular process or an intramolecular one by acetate ligand in the metal coordination shell.
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Due to predominant formation of E product from the less sterically hindered conformer, statistical weights of the two routes leading to E and Z internal olefins are not equal, as the route leading to the Z diastereomer can be neglected.
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