On the mechanism of nucleophilic substitution of allenyl(aryl)iodine(III): Formation of propargyl cation and competition with sigmatropic rearrangement
作者:Masahito Ochiai、Michio Kida、Tadashi Okuyama
DOI:10.1016/s0040-4039(98)01276-3
日期:1998.8
The ratios of nucleophilicsubstitution versus [3,3] sigmatropic rearrangement for the collapse of allenyl(aryl)-iodine(III), generated from the reaction of aryliodanes with propargylsilanes in the presence of BF3Et2O in alcohols, were determined. A proposed mechanism involves generation of propargyl cations from the allenyliodine(III) via a unimolecular pathway.
Synthesis and nucleophilic substitution of allenyl(m-nitrophenyl)iodanes as a new propynyl cation-equivalent species: synthesis of propynyl ethers, esters, and amides
Treatment of diacetoxy(m-nitrophenyl)iodane with propynylsilanes in the presence of BF3·Et2O gives allenyl(m-nitrophenyl)iodanes, which act as propynyl cation-equivalent species and undergo regioselective nucleophilic substitution with alcohols, carboxylic acids and nitriles to give propynyl ethers, esters and amides.