Wang Jiaming, Wang Meng, Wen Yilu, Teng Peng, Li Chenyang, Zhao Changgui
Key Laboratory of Radiopharmaceuticals, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, China.
Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, China.
Org Lett. 2024 Feb 9;26(5):1040-1045. doi: 10.1021/acs.orglett.3c04200. Epub 2024 Jan 31.
An N-heterocyclic carbene (NHC)-catalyzed atroposelective macrolactonization has been disclosed. This approach affords planar-chiral macrocycles in high yields with excellent enantioselectivities over a broad substrate scope. Controlled experiments suggest that the enantioselectivity might arise from the cation- interaction between the acyl azolium and the electron-rich moiety in the substrate. This mechanism is supported by density functional theory calculations, which also suggest an important π-π interaction in stabilizing the transition state.
已公开了一种氮杂环卡宾（NHC）催化的对映选择性大环内酯化反应。该方法能在广泛的底物范围内以高收率和优异的对映选择性得到平面手性大环化合物。对照实验表明，对映选择性可能源于酰基唑鎓与底物中富电子部分之间的阳离子相互作用。密度泛函理论计算支持了这一机理，计算结果还表明在稳定过渡态过程中存在重要的π-π相互作用。
