Key Laboratory of Radiopharmaceuticals, College of Chemistry , Beijing Normal University , Beijing 100875 , China.
J Am Chem Soc. 2019 Jan 30;141(4):1749-1756. doi: 10.1021/jacs.8b12657. Epub 2019 Jan 17.
A highly efficient and enantioselective Rh-( R, R)-f-spiroPhos complex catalyzed hydrogenation of a series of unsaturated sulfones has been developed. With Rh-( R, R)-f-spiroPhos catalyst under mild conditions, not only the asymmetric hydrogenation of both the 3,3-diaryl and exocyclic α,β-unsaturated sulfones was first realized with up to 99.9% ee but also 3-alkyl-3-aryl and benzo[ b]thiophene-1,1-dioxides were successfully hydrogenated to the corresponding chiral sulfones with excellent enantioselectivities (up to 99.4% ee) regardless of the steric hindrance, electronic property, and geometry of the substrates. Moreover, this reaction offers a route to ( S)-(+)- ar-turmerone as a spice flavor, which is an important synthetic intermediate of pharmaceuticals.
一种高效和对映选择性的 Rh-(R,R)-f-spiroPhos 配合物已被开发用于催化一系列不饱和砜的氢化反应。在 Rh-(R,R)-f-spiroPhos 催化剂存在的温和条件下，不仅首次实现了 3,3-二芳基和非环 α,β-不饱和砜的不对称氢化，而且 3-烷基-3-芳基和苯并[b]噻吩-1,1-二氧化物也以优异的对映选择性（高达 99.4%ee）成功氢化得到相应的手性砜，与底物的空间位阻、电子性质和几何形状无关。此外，该反应为（S）-（+）-ar- turmerone 作为香料风味提供了一条途径，它是一种重要的药物合成中间体。
