Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Angew Chem Int Ed Engl. 2020 Apr 20;59(17):6874-6880. doi: 10.1002/anie.201916088. Epub 2020 Mar 3.
Chiral propargyl amines are valuable synthetic intermediates for the preparation of biologically active compounds and functionalized amines. Catalytic methods to access propargyl amines containing vicinal stereocenters with high diastereoselectivity are particularly rare. We report an unprecedented strategy for the synthesis of enantioenriched propargyl amines with two stereogenic centres. An iridium complex, ligated by a phosphoramidite ligand, catalyzes the hydroalkynylation of β,β-disubstituted enamides to afford propargyl amides in a highly regio-, diastereo-, and enantioselective fashion. Stereodivergent synthesis of all four possible stereoisomers was achieved using this strategy.
手性炔丙基胺是制备生物活性化合物和官能化胺的有价值的合成中间体。用于制备含有相邻立体中心的炔丙基胺的催化方法具有高对映选择性的方法特别罕见。我们报告了一种前所未有的策略，用于合成具有两个手性中心的对映体富集的炔丙基胺。手性磷酰胺配体配体的铱配合物可以催化β，β-二取代烯酰胺的氢炔基化反应，以高区域选择性、非对映选择性和对映选择性的方式得到炔丙基酰胺。使用这种策略可以实现所有四种可能的立体异构体的立体发散合成。
