Investigation On O-heterocyclization And Amination Of Alkenes Or Alkynes

Developing new reaction is the eternal theme of organic synthetic chemistry,which brings an endless supply of fresh blood for organic chemistry and provides powerful tools for creacting new materials.Unsaturated hydrocarbon like alkenes and alkynes,have been considered as class of important commodity in petrochemical and coal chemical industry,which occupies an important position in the national economy.At the same time,alkenes and alkynes is also the basis for the creation of new substances,which greatly accelerates the development of chemistry branch,especially for organic chemistry,and make tremendous contribution to the material civilization and spiritual civilization of human beings.The distribution of oxygen heterocyclic compounds and nitrogen-containing function molecules in nature is very wide.Quite a few of these compounds play a significant physiological role in plant and animal species,and has been indispensable in human life activities.Simultaneously,these function molecules can also be widely applied in fields fine chemicals,such as adhesive,catalysts,food and feed additives,commodity chemicals,dye and coating,et al.Therefore,the development for the efficient synthesis of these function molecules,not only enriched the essence of organic synthesic chemistry,but also provides scientific and technical support for the progress in chemical and chemical engineering,pharmaceutical,pesticide and functional materials.Based on it,this thesis studied high catalytic efficiency,high selectivity,and high atom economy for the synthesis of oxygen heterocyclic compounds and nitrogen-containing function molecules with alkenes and alyenes,the details are as follows:?1?Copper-promoted cyclization of carbon dioxide and propargylic alcohols for the synthesis of?E?-?-iodoalkylidene cyclic carbonates.With the use of Cu?OTf?₂ as the promoter,in the presences of KI,?E?-?-iodoalkylidene cyclic carbonates was synthesized in high chemo-and stereoselective for the coupling of carbon dioxide and propargylic alcohols,thus realizing the utilization of carbon dioxide in chemistry.?2?Base-promoted formal[4+3]annulation between 2-fluorophenylacetylenes and ketones for the assembly of benzoxepines.The reaction proceeds through a tandem?-vinylation of ketones followed by an intramolecular nucleophilic aromatic substitution?S_NAr?reaction of the in situ generated?,?-unsaturated ketone intermediates,providing a straightforward access to a wide range of functionalized benzoxepines in moderate to high yields.The transition-metal-free methodology featured a wide substrate scope,the use of easily available starting materials,and a high functional group tolerance.?3?Palladium-catalyzed oxidative amination of vinyl ethers with hydrogen peroxide to afford?-amino acid esters.With anilines and vinyl ethers as starting materials,Pd?OAc?₂ as catalyst,hydrogen peroxide as the green oxidant,?-amino acid esters were generated via this catalyst system.Also,this reaction was characterized by the simplicity of the experimental procedure,mild reaction conditions,high atom economy.?4?Pd-Catalyzed three-component reaction of anilines,ethyl vinyl ether,and nitro-paraffin to generate??Nitroamines.We established a novel Pd-catalyzed aza-Henry reaction with simple and readily available materials to give various important organic molecules?-nitroamines.Whenthisreactionproceedswithmorpholine,?-alkyl-?-nitroamines was receved,while DABCO was added to this catalyst system,it will led to the unexpected rearrangement to afford?-methyl-?-nitroamines.?5?Palladium-catalyzed oxidative amination of homoallylic alcohols for the synthesis of?-amino ketones.The synthetic utility of the reaction can be performed by installing the carbonyl and amino groups along an alkyl chain in one step,offering several advantages such as simple starting materials and easy operation.The formation of C-N and C=O bond is quite different from previous Heck reaction or redox-relay Heck reaction,which is a new process for the oxidative amination of alkenols.