| Title | Enantioselective Formal Vinylogous N-H Insertion of Secondary Aliphatic Amines Catalyzed by a High-Spin Cobalt(II) Complex |
| Authors | Yang, Wei Pu, Maoping Lin, Xiaobin Chen, Min Song, Yanji Liu, Xiaohua Wu, Yun-Dong Feng, Xiaoming |
| Affiliation | Sichuan Univ, Coll Chem, Key Lab Green Chem & Technol, Minist Educ, Chengdu 610064, Peoples R China Shenzhen Bay Lab, Shenzhen 518055, Peoples R China Peking Univ Shenzhen Grad Sch, Lab Computat Chem & Drug Design, State Key Lab Chem Oncogen, Shenzhen 518055, Peoples R China |
| Keywords | CARBENE INSERTION CYCLOADDITION ESTERS RHODIUM BONDS ACIDS REARRANGEMENT PALLADIUM NITRONES LIGANDS |
| Issue Date | 30-Jun-2021 |
| Publisher | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY |
| Abstract | Vinylcarbene insertion into the nitrogen-hydrogen (N-H) bond of amines allows direct access to alpha,beta-unsaturated gamma-amino acid derivatives, meeting a marked challenge in the control of regio- and enantioselectivities. Here, we report a highly gamma-selective and enantioselective insertion into N-H bonds of aliphatic or aromatic secondary amines with vinyl substituted alpha-diazo pyrazoleamides using a high-spin chiral N,N'-dioxide/cobalt(II) complex catalyst. The method affords a wide variety of valuable optically active Z- and E-type vinyl gamma-amino amides. Calculation reveals a spin state change from the quartet cobalt(II) complex to a doublet Co(II)-carbene species for facile Z-selective and enantioselective nucleophilic addition. |
| URI | http://hdl.handle.net/20.500.11897/618728 |
| ISSN | 0002-7863 |
| DOI | 10.1021/jacs.1c04367 |
| Indexed | SCI(E) |
| Appears in Collections: | 深圳研究生院待认领 |
