Zhang Rongxing, Zhou Qinghai, Wang Xin, Xu Lanting, Ma Dawei
Chang-Kung Chuang Institute, School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuang Lu, Shanghai, 200062, China.
The Education Ministry Key Lab of Resource Chemistry, Joint International Research Laboratory of Resource Chemistry of Ministry of Education, Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Frontiers Science Center of Biomimetic Catalysis, College of Chemistry and Materials Science, Shanghai Normal University, Shanghai, 200234, China.
Angew Chem Int Ed Engl. 2023 Dec 4;62(49):e202312383. doi: 10.1002/anie.202312383. Epub 2023 Nov 6.
The (S)-nobin-embodied picolinamide and L-hydroxyproline-derived amide are effective ligands for Cu-catalyzed enantioselective coupling reaction of (hetero)aryl iodides with α-alkyl substituted cyanoacetates. This arylation reaction gave α-(heteroaryl)-α-alkyl cyanoacetates in good to excellent enantioselectivities (up to 95 % ee). A variety of functionalized (hetero)aryl and alkyl groups could be introduced to the quaternary center and therefore provided a valuable tool for preparing enantioenriched compounds with an all-carbon quaternary center tethered with convertible functional groups. The size of both α-alkyl and ester groups was proven as the key factor for asymmetric induction.
(S)-诺宾（nobin）衍生的吡啶酰胺和L-羟基脯氨酸衍生的酰胺是用于铜催化的（杂）芳基碘化物与α-烷基取代的氰基乙酸酯的对映选择性偶联反应的有效配体。该芳基化反应以良好至优异的对映选择性（高达95％ee）生成α-（杂芳基）-α-烷基氰基乙酸酯。各种官能化的（杂）芳基和烷基可以引入到季碳中心，因此为制备具有与可转化官能团相连的全碳季碳中心的对映体富集化合物提供了有价值的工具。α-烷基和酯基的大小被证明是不对称诱导的关键因素。
