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

页码：15387 / 15391

页数：5

共 80 条

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