Studies On The Transition-metal Catalyzed C-H Functionalization To Construct Isoquinoline And 2-Aminoindole Derivatives

Isoquinolines and indoles are two important compounds in heterocyclic compounds,which are the core skeletons of many natural products,bioactive molecules and functional materials.They are widely used in medicines,materials,dyes,etc.In the past few years,transition-metal catalyzed C-H functionalization has aroused much attention,and is widely applied in the synthesis of various compounds and their functionalization.This paper launches an investigation on the synthetic methodology of substituted isoquinolines and regioselective amidation of indoles at the C2-position,and falled into three parts as follows.1.A review of sulfoxonium ylide including its preparation,typical reactions and their application in carbeniod transfer reactions with transition-metal catalysis was discussed.Combining the current situation of sulfoxonium ylide as a carbene synthon leads to the first work of this topic.2.A direct C-H functionalization/annulation cascade reaction of benzimidates and sulfoxonium ylides,which is used as a carbene synthon,under the catalysis of[Ru?p-cymene?Cl₂]₂ is disclosed.The reaction proceeds smoothly with a broad range of substrates,giving access to a variety of isoquinoline derivatives in moderate to good yields using an organic acid additive under oxidant free conditions.3.Regioselective amidation of N-protected free indoles at C2-position is achieved in the presence of Cp*Co?CO?I₂ under the direction of ketone group installed at C3-position.By using oxazolones as the source of amide group,with AgSbF₆ and Adm-1-COOH as additive,2-aminoindole derivatives were synthesized in high regioselectivities,good functional group tolerance with moderate to excellent yields.The following experimental controls and deuteration experiments lend support to the proposed mechanism.