Asymmetric Rh(II)/Pd(0) Relay Catalysis: Synthesis of α-Quaternary Chiral β-Lactams through Enantioselective C–H Insertion/Diastereoselective Allylation of Diazoamides
作者:Liang-Zhu Huang、Zi Xuan、Hyun Ji Jeon、Zhen-Ting Du、Ju Hyun Kim、Sang-gi Lee
DOI:10.1021/acscatal.8b01687
日期:2018.8.3
α-quaternary chiral β-lactam moiety via Rh(II)/Pd(0)-catalyzed stereoselective relay catalytic reaction is reported. This asymmetric dual relay catalysis involves Rh(II)-catalyzed enantioselective intramoluecular C–H insertions of α-diazoamides, and sequential Pd(0)-catalyzed diastereoselective intermolecular allylic alkylation. Under mild reaction conditions, a broad range of α-quaternary allylated chiral
据报道,通过Rh(II)/ Pd(0)催化的立体选择性中继催化反应,可直接构建α-季手性β-内酰胺部分。这种不对称的双重中继催化涉及Rh(II)催化的α-重氮酰胺的对映选择性分子内C–H插入,以及顺序的Pd(0)催化的非对映选择性分子间烯丙基烷基化。在温和的反应条件下,已以高收率(高达99%)和优异的立体选择性合成了多种α-季烯丙基手性β-内酰胺[对映异构体比率(dr)> 99:1,对映体高达98%超额(ee)]。