Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090, Vienna, Austria.
Institute of Theoretical Chemistry, University of Vienna, Währinger Strasse 17, 1090, Vienna, Austria.
Angew Chem Int Ed Engl. 2017 Feb 13;56(8):2212-2215. doi: 10.1002/anie.201610105. Epub 2017 Jan 18.
A general, asymmetric redox arylation of ynamides and thioalkynes with chiral sulfoxides is reported. This is the first example of a general 1,4-chirality transfer from sulfur to a carbon stereocenter through a sulfonium [3,3]-sigmatropic rearrangement. This reaction delivers α-arylated thioesters and amides under mild conditions in an atom-economical manner. The products are formed in high yields with enantiomeric ratios up to 99.5:0.5. Quantum chemical calculations suggest a mechanism for the chirality transfer from sulfur to carbon and explain the experimentally observed correlation of the enantioselectivity with both the catalyst and the substrate.
本文报道了手性亚砜参与的炔酰胺和硫代炔烃的不对称氧化芳基化反应。这是首例通过硫翁[3,3]-σ重排将 1,4-手性从硫原子转移到碳原子立体中心的通用方法。该反应在原子经济性条件下以温和的方式提供了α-芳基化硫酯和酰胺。产物以高收率和高达 99.5:0.5 的对映选择性形成。量子化学计算为硫到碳的手性转移提供了一种机制，并解释了实验观察到的对映选择性与催化剂和底物的相关性。
