Rh(?)-catalyzed Direct C-7 Amination Of Indolines With Anthranils

Indole and indoline scaffolds widely occur in bioactive reagents,medicine,and agricultural chemicals for their unique properties.Their synthesis and chemical modification have attracted more and more attention from chemical workers.Recently,due to its good atomic economy and high conversion rate,transition-metal catalyzed C-H bond functionalization has been a powerful tool in synthetic chemistry.Therefore it is of great importance to develop Rh-catalyzed direct C-H functionalization.In this manuscript,on the base of previous reports and pre-experiment,for Rh-catalyzed direct C-7 amination of indolines,some works have been done as follows:?1?By the screening of catalysts,additives,solvent and reaction temperature etc.in the reaction of 1-?pyrimidin-2-yl?indoline with anthranil,the optimal reaction conditions have obtained.?2?With the optimized conditions in hand,the substrate scope,efficiency and regioselectivity for Rh?III?-catalyzed direct C-7 amination of various indolines was evaluated by use of anthranils as the aminating reagents.?3?On the basis of precedent reports and the control experimental results,by the careful analysis of products,byproducts and possible reaction intermediate,a plausible mechanism was proposed.Eventually,we developed a simple and facile method for the direct C-7 amination of indolines with anthrnails via Rh?III?-catalyzed C-H activation by using readily available,high atom-economy substituted anthrnails as the aminating regent,[RhCp*Cl₂]₂/AgSbF₆ as the catalyst system.The reactions delivered corresponding indolines with high efficiency under mild conditions,while no external oxidants were required.The amino group and carbonyl group of the desired products enable the possibility for the elaboration and construction of diverse and bioactive C-7aminated indoline derivatives.