New Type Hiyama Coupling Reaction Of Arylsilanes Catalysed By Palladium

Organosilicon reagents have shown many unique advantages in organic synthesis,including low price,high stability,environmental benignity and easy operation.The application of organosilicon reagents in organic synthesis would greatly promote the vigorous development of organic chemistry,especially the application of C-C bond and C-X bond construction which was an important research hotspot.Based on the previous works,this dissertation focused on one of the organosilicon reagents---arylsilanes which is new developed in last 10 years.The important progress of the arylsilanes applied to synthesis chemistry was reviewed,including the application for constructing Csp~2-Csp~2,Csp~2-Csp~3,Csp~2-Csp and C-X bond catalyzed by transition-metal.Thus,we further aimed to develop the new coupling reaction of arylsilanes,including the new method for arylation through C-H bond activation and Ar-P construction.The results were as following:1.A palladium(?)-catalyzed method for C-7 arylation of indoline with arylsilane were achieved and a series of C-7 arylation of indoline directed by carbonyl on the N atom of indoline was synthesized.This protocol carried on directly by C-H activation instead of prefunctional of indoline C-7 position to construct C-C bond,and the feature of this reaction shows a good compatibility and gentle.C-7 arylation indole compounds were obtained when the products detach the carbonyl by base and then oxidized by DDQ.2.A palladium(?)-catalyzed method for construct Ar-P bond using arylsilane as starting material oxidative cross-coupling reaction has been described.It showed advantages of good functional group tolerance and wild reaction condition.With the optimized reaction conditions,a series of aromatic phosphate derivatives were synthesized.