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 s...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.展开更多
Privileged biaryl frameworks,BINOL and NOBIN,were efficiently constructed with sole 1-DNQs as arylation reagents under one set of reaction conditions.The judicious selection of palladium-catalytic system plays a pivot...Privileged biaryl frameworks,BINOL and NOBIN,were efficiently constructed with sole 1-DNQs as arylation reagents under one set of reaction conditions.The judicious selection of palladium-catalytic system plays a pivotal role in the excellent selectivities.This transformation accommodated fairly broad substrate generality for both 2-naphthol and N-Boc-2-naphthylamine and afforded the structurally diversified BINOLs and NOBIN derivatives in high efficiency.Notably,the bromosubstituents which cannot survive in conventional palladium-catalyzed reactions were well-compatible with this set of conditions,providing an effective handle for further enriching the library of BINOLs and NOBINs.Preliminary attempts on the asymmetric variant of this reaction were also performed with up to 80:20 er for BINOLs synthesis.展开更多
基金support from the National Key R&D Program of China (2022YFA1503703,2021YFF0701604)the National Natural Science Foundation of China (21825105,22231004,22271135)+1 种基金Guangdong Innovative Program (2019BT02Y335)Shenzhen Science and Technology Program (KQTD20210811090112004,JCYJ20210324120205016,JCYJ20210324105005015).
文摘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.
基金supported by the National Natural Science Foundation of China(21825105)the Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)+2 种基金the Guangdong Innovative Program(2019BT02Y335)the Shenzhen Nobel Prize Scientists Laboratory Project(C17213101)the SUSTech Special Fund for the Construction of High-Level Universities(G02216402)。
文摘Privileged biaryl frameworks,BINOL and NOBIN,were efficiently constructed with sole 1-DNQs as arylation reagents under one set of reaction conditions.The judicious selection of palladium-catalytic system plays a pivotal role in the excellent selectivities.This transformation accommodated fairly broad substrate generality for both 2-naphthol and N-Boc-2-naphthylamine and afforded the structurally diversified BINOLs and NOBIN derivatives in high efficiency.Notably,the bromosubstituents which cannot survive in conventional palladium-catalyzed reactions were well-compatible with this set of conditions,providing an effective handle for further enriching the library of BINOLs and NOBINs.Preliminary attempts on the asymmetric variant of this reaction were also performed with up to 80:20 er for BINOLs synthesis.
