Study On C-H Functionalization Catalyzed By Ru(Ⅱ) And Related Reactions

This thesis mainly studies the functionalization and related reactions of ortho-CH bonds via Ru(Ⅱ)-catalyzed C-H activation,and develops a catalytic,mild,and efficient regioselective synthesis method,and the synthesis of hydroxymethylated indole derivatives and a series of allene compounds was successfully realized at the C7 position.In addition,we have achieved a one-pot method to directly synthesize the more useful C7-formylated indole product,and to expand the range of substrates to achieve the allenylation of anilines and phenol compounds other than indoline can obtain a series of more valuable allene products.The main contents are as follows:(1)Using indolinoline as the template substrate and formaldehyde as the source of methylol,the optimization of the hydroxymethylation reaction conditions at C7 of indololine were performed,and then investigation of substrate suitability and tolerance.While,some derivatization experiments and mechanism exploration experiments were performed on the reaction to increase the practicality of the methodology and further research and application of the method.It is worth noting that,with a one-pot method,DDQ can be used as an oxidant to directly synthesize a more useful C7-formylated indole product;(2)The ortho-C-H allenylation of electron-rich benzene derivatives with propargyl alcohol derivatives has always been a challenging study,mainly due to the inherent para-SN2’-type substitution process which affects the activation of the ortho C-H bond.To explore the regioselective ortho-C-H allenylation of electron-rich aniline(indoline)and phenol derivatives catalyzed by Ru(Ⅱ),making ortho-alkylation of aniline and phenol derivatives possible,and the reaction has a wide range substrate suitability.Highly active chiral transfer can also be used to prepare substituted allene compounds with high optical activity(ee value ≥95%).In the existing catalytic systems,no para-allenylation products have been observed,showing the complete opposite regional selectivity.In general,compared with the traditional synthesis methods in the past,it is an effective way to realize the indole C7 functionalization via transition metal Ru(Ⅱ)-catalyzed C-H activation,with high efficiency,simplifies the experimental steps,fast and accurate positioning.The development and in-depth study of its application in industrial production will have unparalleled advantages and potentials,which will provide tremendous help to human chemistry and medicine.