Ma Zhaoming, Xu Wenqiang, Wu Yun-Dong, Zhou Jianrong Steve
State Key Laboratory of Chemical Oncogenomics, Guangdong Provincial Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, 2199 Lishui Road, Nanshan District, Shenzhen 518055, China.
Laboratory of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen 518055, China.
J Am Chem Soc. 2023 Aug 2;145(30):16464-16473. doi: 10.1021/jacs.3c02829. Epub 2023 Jul 21.
Cobalt complexes of chiral pyrox ligands catalyzed enantioselective reductive couplings of nonconjugated iododienes with aryl iodides or alkenyl bromides. The reaction enabled stereoselective syntheses of 5-7-membered azacycles carrying quaternary stereocenters. Mechanistically, cross-electrophile selectivity originated from selective coupling of alkylcobalt(I) complexes generated after cyclization with aryl iodides.
手性吡咯配体的钴配合物催化非共轭碘代二烯与芳基碘化物或烯基溴的对映选择性还原偶联反应。该反应能够立体选择性地合成带有季碳立体中心的5至7元氮杂环。从机理上讲,交叉亲电试剂选择性源于环化后生成的烷基钴(I)配合物与芳基碘化物的选择性偶联。