An Enantioselective Bidentate Auxiliary Directed Palladium-Catalyzed Benzylic C-H Arylation of Amines Using a BINOL Phosphate Ligand

被引：128
作者：
Wang, Hao [1 ,2 ]
Tong, Hua-Rong [1 ,2 ]
He, Gang [1 ,2 ]
Chen, Gong [1 ,2 ,3 ]
机构：
[1] Nankai Univ, Ctr Chem Sci & Engn Tianjin, State Key Lab, Tianjin 300071, Peoples R China
[2] Nankai Univ, Ctr Chem Sci & Engn Tianjin, Inst Elemento Organ Chem Collaborat Innovat, Tianjin 300071, Peoples R China
[3] Penn State Univ, Dept Chem, University Pk, PA 16802 USA
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 49期
关键词：
arylations; C-H activation; enantioselectivity; palladium; reaction mechanism; KEY MECHANISTIC FEATURES; C(SP(3))-H BONDS; ALPHA-ALLYLATION; METAL CATALYSIS; ACTIVATION; ALKYLATION; ACID; FUNCTIONALIZATION; C(SP(2))-H; COMPLEXES;
D O I：
10.1002/anie.201609337
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
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 -C-H arylations of alkyl amines, and proceeds with up to 97% ee. The 2,2-dihydroxy-1,1-binaphthyl (BINOL) phosphoric acid ligand, Cs2CO3, 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.
引用
收藏
页码：15387 / 15391
页数：5
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