The formation of α-phenyl-β-halovinyl cation, β-phenyl-α-halovinyl cation, and also the halogen-bridged and the spirocyclic phenyl-bridged cations, as intermediates of protonation of phenylethynyl halides, or of halogen addition to phenylethynes, has been evaluated by DFT at the B3LYP/6-31+G(d) level and, for comparison in representative cases, by B3LYP/6-311++G(d,p). 1 Structural and mechanistic studies of the lithium diisopropylamide (LDA)-mediated anionic Fries rearrangements of aryl carbamates have been described. 2 Substituents at the meta position of the arene (H, OMe, F) and the dialkylamino moiety of the carbamate (Me 2 N, Et 2 N, and i-Pr 2 N) markedly influence the relative rates of ortholithiation and subsequent Fries rearrangement. The mechanism of the Fries rearrangement of aryl formates promoted by boron trichloride has been studied by means of 1 H, 2 H, and 11 B NMR spectroscopy and DFT calculations. 3 After the formation of a 1:1 substrate -Lewis acid adduct, the rearrangement proceeds in two steps, beginning with the cleavage of the ester bond and the release of formyl chloride in situ, which, in turn, acts as a formylating agent, introducing 451
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