School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing 210014, China.
J Org Chem. 2011 Oct 21;76(20):8488-94. doi: 10.1021/jo201347r. Epub 2011 Sep 20.
Intramolecular oxygen transfer of nitrone- and sulfoxide-alkynes was achieved using a catalytic amount of Au(I) and a stoichiometric amount of iodine. The Au(I)-catalyzed cyclization of a nitrone-terminal alkyne afforded a cyclic iminoester, while cyclization of analogous nitrone-internal alkynes yielded aldehyde-enones. The I(2)-mediated cyclization of nitrone-alkynes afforded iodinated γ-lactams and the I(2)-mediated internal redox of the closely related sulfoxide-alkynes gave diketones functionalized with a thoiether.
使用催化量的金(I)和化学计量的碘实现了亚硝酮和亚砜炔的分子内氧转移。亚硝酮末端炔的 Au(I)催化环化生成环状亚氨基酯，而类似的亚硝酮内炔的环化生成醛烯酮。亚硝酮炔的 I(2)介导环化生成碘化γ-内酰胺，而相关的亚砜炔的 I(2)介导的内部氧化还原反应生成了噻吩醚官能化的二酮。
