手性磷酸硼配合物与水形成的手性布朗斯特酸：吲哚的不对称还原反应
Chiral Brønsted Acid from Chiral Phosphoric Acid Boron Complex and Water: Asymmetric Reduction of Indoles.
作者信息
Yang Kai, Lou Yixian, Wang Chenglan, Qi Liang-Wen, Fang Tongchang, Zhang Feng, Xu Hetao, Zhou Lu, Li Wangyang, Zhang Guan, Yu Peiyuan, Song Qiuling
机构信息
Key Laboratory of Molecule Synthesis and Function Discovery, Fujian Province University, College of Chemistry at Fuzhou University, Fuzhou, Fujian, 350108, China.
Collaborative Innovation Center of Yangtze River Delta Region Green Pharmaceuticals, Zhejiang University of Technology, Hangzhou, Zhejiang, 310000, P. R. China.
出版信息
Angew Chem Int Ed Engl. 2020 Feb 17;59(8):3294-3299. doi: 10.1002/anie.201913656. Epub 2020 Jan 9.
A new chiral Brønsted acid, generated in situ from a chiral phosphoric acid boron (CPAB) complex and water, was successfully applied to asymmetric indole reduction. This "designer acid catalyst", which is more acidic than TsOH as suggested by DFT calculations, allows the unprecedented direct asymmetric reduction of C2-aryl-substituted N-unprotected indoles and features good to excellent enantioselectivities with broad functional group tolerance. DFT calculations and mechanistic experiments indicates that this reaction undergoes C3-protonation and hydride-transfer processes. Besides, bulky C2-alkyl-substituted N-unprotected indoles are also suitable for this system.
一种由手性磷酸硼（CPAB）络合物和水原位生成的新型手性布朗斯特酸成功应用于不对称吲哚还原反应。这种“定制酸催化剂”，如密度泛函理论计算所示，其酸性比对甲苯磺酸更强，能够实现前所未有的C2-芳基取代的N-未保护吲哚的直接不对称还原，具有良好至优异的对映选择性以及广泛的官能团耐受性。密度泛函理论计算和机理实验表明，该反应经历C3-质子化和氢化物转移过程。此外，位阻较大的C2-烷基取代的N-未保护吲哚也适用于该体系。
Zotero 插件