State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation, Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin, 300071, China.
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania, 16802, USA.
Angew Chem Int Ed Engl. 2016 Dec 5;55(49):15387-15391. doi: 10.1002/anie.201609337. Epub 2016 Nov 11.
A new enantioselective palladium(II)-catalyzed benzylic C-H arylation reaction of amines is enabled by the bidentate picolinamide (PA) directing group. This reaction provides the first example of enantioselective benzylic γ-C-H arylations of alkyl amines, and proceeds with up to 97 % ee. The 2,2'-dihydroxy-1,1'-binaphthyl (BINOL) phosphoric acid ligand, Cs CO , and solvent-free conditions are essential for high enantioselectivity. Mechanistic studies suggest that multiple BINOL ligands are involved in the stereodetermining C-H palladation step.
一种新的对映选择性钯 (II)-催化的胺的苄基 C-H 芳基化反应可以通过双齿吡啶甲酰胺 (PA) 导向基团来实现。该反应提供了首例对映选择性苄基γ-C-H 芳基化的烷基胺的例子，产率高达 97%ee。2,2'-二羟基-1,1'-联萘基 (BINOL) 磷酸配体、Cs CO 3 和无溶剂条件对于高对映选择性是必不可少的。机理研究表明，多个 BINOL 配体参与了立体决定的 C-H 钯化步骤。
