Metal-Catalyzed/β-oxygen Elimination Triggered Synthesis Of Isoquinolines

β-oxygen elimination is an elemental reaction in organometalic chemistry.The metal-catalyzed reactions through β-oxygen elimination can effectively construct easily transformed unsaturated bonds,and therefore has attracted extensive attention from the synthetic communities.In recent years,substantial progress has been made in C-H bond allylations promoted by β-oxygen,which has gradually become ideal methods for the construction of allyl fragments regarding to efficiency and redox-neutral nature.The thesis mainly studied metal-catalyzed synthesis of isoquinolinones via β-oxygen elimination,including Rh(III)catalyzed C-H allylation/annulative Markovnikov addition reactions for the synthesis of isoquinolinones containing a C3 quaternary center using 5-methylene-1,3-dioxane-2-one as the allylation reagent;Cobaltcatalyzed/carboxylic acid promoted vinyl transfer reactions to synthesize nonsubstituted isoquinolinones via β-oxygen elimination.The thesis is composed of three sections:1.The progress of C-H allylations catalyzed by transition metals and their applications for the synthesis of hetero Cyclics are reviewed in detail.C-H allylation reactions has been developing rapidly in recent years,which has also been extended to cyclic carbonates.The appilcations of those trasnformations to prepare hetero Cyclic compounds are growing widely,especially nitrogen containing hetero Cyclics.Therefore,the development of metal-catalyzed transformations cyclic carbonates for the rapid constructions of hetero Cyclics is of great significance for the synthetical communities.2.A Rh(III)catalyzed C-H allylation/cyclization C-H allylation/annulative Markovnikov addition reactions promoted by β-oxygen elimination with 5-methylene-1,3-dioxane-2-one was developed.Isoquinolinone derivatives containing a C3 quaternary center could be synthesized effectively under mild reaction conditions.The ingenious use of β-oxygen elimination to form allyl alcohol fragment enabled the successive Markovnikov addition to o Ccur,affording the C3 quaternary center.US28 reverse agonist analogues were synthesized within three steps by untilizing the C-H allylation/annulative Markovnikov addition reaction as the key.3.We found that carboxylic acid can effectively promote the vinyl transfer reactions catalyzed by Co(III)-complex through β-oxygen elimination.When 2,6-dimethylbenzoic acid was added as an additive,the reaction showed high catalytic activity and good functional group tolerance with only 3 mol% of Co(III)catalyst.We will clarify the reason why carboxylic acid promoted the reaction by kinetic studies and DFT calculations.In this dissertation,we established effective methods for the construction of isoquinolinones by metal-catalyzed C-H functionalization through β-oxygen elimination,developed a new allyl reagent,and found carboxylic acid could dramatically reduce the loading of catalyst and promote vinyl transfer reactions.