Teng Ming-Ya, Wu Yong-Jie, Chen Jia-Hao, Huang Fan-Rui, Liu De-Yang, Yao Qi-Jun, Shi Bing-Feng
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China.
College of Material Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou, 311121, Zhejiang, China.
Angew Chem Int Ed Engl. 2024 Mar 4;63(10):e202318803. doi: 10.1002/anie.202318803. Epub 2024 Jan 24.
Transition metal-catalyzed enantioselective C-H carbonylation with carbon monoxide, an essential and easily available C1 feedstock, remains challenging. Here, we disclosed an unprecedented enantioselective C-H carbonylation catalyzed by inexpensive and readily available cobalt(II) salt. The reactions proceed efficiently through desymmetrization, kinetic resolution, and parallel kinetic resolution, affording a broad range of chiral isoindolinones in good yields with excellent enantioselectivities (up to 92 % yield and 99 % ee). The synthetic potential of this method was demonstrated by asymmetric synthesis of biological active compounds, such as (S)-PD172938 and (S)-Pazinaclone. The resulting chiral isoindolinones also serve as chiral ligands in cobalt-catalyzed enantioselective C-H annulation with alkynes to construct phosphorus stereocenter.
利用一氧化碳进行过渡金属催化的对映选择性C-H羰基化反应仍然具有挑战性,一氧化碳是一种重要且易于获得的C1原料。在此,我们报道了一种前所未有的对映选择性C-H羰基化反应,该反应由廉价且易于获得的钴(II)盐催化。反应通过去对称化、动力学拆分和平行动力学拆分高效进行,以良好的产率和优异的对映选择性(产率高达92%,对映体过量值高达99%)提供了多种手性异吲哚啉酮。该方法的合成潜力通过生物活性化合物(如(S)-PD172938和(S)-帕齐那克隆)的不对称合成得到了证明。所得的手性异吲哚啉酮还可作为手性配体用于钴催化的与炔烃的对映选择性C-H环化反应,以构建磷立体中心。