Davenport Research Laboratories, Department of Chemistry, University of Toronto, Toronto, Ontario, M5S 3H6, Canada.
Angew Chem Int Ed Engl. 2017 Sep 18;56(39):11927-11930. doi: 10.1002/anie.201704922. Epub 2017 Aug 14.
A rhodium-Josiphos(L*) catalyzed enantioselective intramolecular hydroarylation reaction is described. The reductive cyclization of o-bromoaniline-derived acrylamides provides convenient access to 3,3-disubstituted oxindoles in good yields and with excellent enantioselectivity across a range of substrates. We propose that the key cyclization proceeds via a rhodium(III) intermediate. Overall, this method represents an unusual mode of reactivity for rhodium catalysis and is complementary to palladium(0)-catalyzed α-arylation methods.
描述了一种铑-Josiphos（L*）催化的对映选择性分子内氢芳基化反应。邻溴苯胺衍生的丙烯酰胺的还原环化反应以良好的收率和优异的对映选择性提供了方便的 3,3-二取代氧化吲哚，适用于多种底物。我们提出关键的环化反应通过铑（III）中间体进行。总的来说，这种方法代表了铑催化的一种不寻常的反应模式，与钯（0）催化的α-芳基化方法互补。
