Atroposelective Synthesis of 2-Arylindoles via Chiral Phosphoric Acid-Catalyzed Direct Amination of Indoles  

作　　者：Wen Bao Ye-Hui Chen Yu-Wei Liu Shao-Hua Xiang Bin Tan 

机构地区：[1]School of Pharmacy&StateKey Laboratory of Applied Organic Chemistry,Lanzhou University,Lanzhou,Gansu 730000,China [2]Shenzhen Grubbs Institute,Department of Chemistry,Southern University of Science and Technology,Shenzhen,Guangdong 518055,China

出　　处：《Chinese Journal of Chemistry》2024年第7期731-735,共5页中国化学（英文版）

基　　金：support from the National Key R&D Program of China (2022YFA1503703,2021YFF0701604);the National Natural Science Foundation of China (21825105,22231004,22271135);Guangdong Innovative Program (2019BT02Y335);Shenzhen Science and Technology Program (KQTD20210811090112004,JCYJ20210324120205016,JCYJ20210324105005015).

摘　　要：Indole-based atropisomers are a very important class of axially chiral compounds.However,the atroposelective synthesis of axially chiral 2-arylindole remains largely unexplored.In this study,we report the successful synthesis of atropisomeric 2-arylindoles using direct amination of indoles with p-quinonediimines in the presence of chiral phosphoric acid as a catalyst.Quinonediimine acts as an aminating reagent through formal polarity inversion of imine.The malonate group on the 2-aryl of 2-indoles was found to be essen-tial for high enantioselectivity of the products.This could be due to the additional interaction between the ester group and the cata-lyst,as well as the intramolecular hydrogen bonding.Our findings provide a new strategy for the asymmetric construction of 2-arylindole atropisomers.

关 键 词：Chiral phosphoric acid Quinonediimines Direct amination Nucleophilic addition Asymmetric catalysis Enantioselectivity Axially chiral 2-arylindole Atroposelective synthesis 

分 类 号：O62[理学—有机化学]