State Key Laboratory of Drug Research , Shanghai Institute of Materia Medica, Chinese Academy of Sciences , 555 Zuchongzhi Road , Shanghai 201203 , China.
University of Chinese Academy of Sciences , Beijing 100049 , China.
Org Lett. 2018 Apr 6;20(7):1789-1793. doi: 10.1021/acs.orglett.8b00289. Epub 2018 Mar 13.
A site-selective rhodium-catalyzed asymmetric 1,4-/1,2-addition of arylboronic acids to challenging α,β-unsaturated cyclic ketimines was realized through a ligand-controlled strategy. By employing different chiral olefin ligands, a ligand-controlled switch in the reaction regioselectivity was attained for the first time. The reactions allow the synthesis of highly valuable α,α-disubstituted chiral allylic amines and enantioenriched 1,4-adducts. Further product transformation provided easy access to various quaternary carbon-containing chiral amines and amino acid derivatives bearing multifunctional groups.
通过配体控制策略，实现了通过铑催化的芳基硼酸对具有挑战性的α,β-不饱和环酮亚胺的位点选择性不对称 1,4-/1,2-加成。通过使用不同的手性烯烃配体，首次实现了反应区域选择性的配体控制开关。该反应允许合成高价值的α,α-二取代手性烯丙基胺和对映体富集的 1,4-加合物。进一步的产物转化提供了获得各种含有季碳原子的手性胺和带有多功能基团的氨基酸衍生物的简便途径。
