Study On The Alkenes Participation In The Synthesis Of Oxazoles,Benzoyl Isoquinolines And Selenium Alcohols

Developing the reactions of unsaturated hydrocarbons(including olefins,alkynes and aromatics,etc.)is one of the focus of coal chemical and petrochemical development,which plays an important role in our economic development.It also has a major impact on sustainable development in our country.In the history of the development of chemistry,the functionalization reaction of unsaturated hydrocarbon has a great role in promoting the progress of industrial development and has always been one of the hot areas to be studied,which is an important means to create new substances.Until now,there are nine Nobel Prize in Chemistry awarded to the research groups who dedicated to the researchs involved in the conversion of unsaturated hydrocarbons,in recognition of their outstanding contributions in developing "efficient,environmentally friendly and atom economy" concept in an unsaturated hydrocarbon substance transformation.In 2010,the palladium catalyzed Heck-type reaction,recognized with Nobel Prized,has become a powerful tool to prepare substituted olefins,which is widely used in the total synthesis of natural products and Drug Synthesis.In this context,we reported the synthesis of oxazole,benzoyl isoquinolines and selenium alcohols compounds starting from alkenes.(1)Organic azide is a common type of 1,3-dipole coupling with unsaturated carbon-carbon bonds to conduct[3+2]cycloaddition reaction,which is a common method of constructing nitrogenous heterocyclic compounds.As we all know,organic azide and carbon-carbon triple bond in the transition metal-catalyzed[3+2]cycloaddition is a classic reaction to synthesize triazole compounds.However,there are few papers to report utilizing azide coupling with alkenes to build heterocyclic compounds selectively.Compared with alkynes,alkenes coupling with azide to form triazolinone is unstable and the non-aromatic structure can easily open the ring to release nitrogen molecule.Therefore,it is difficult to synthesize nitrogenous heterocyclic compounds.In this report,we developed a novel and efficient approach to 2,5-disubstituted oxazoles.This cascade reaction employs naturally abundant air as the sole oxidant as well as the oxygen source and generates nitrogen and water as by-products.This method requires only catalytic amounts of CuCl,mild reaction conditions,and has good yields.(2)C1-benzoyl isoquinolines are extensive distributed in natural products and commercial drugs.Consequently,a large number of papers about synthesis of C1-benzoyl isoquinolines were reported,such as classic nucleophilic addition with Grignard reagent,metalorganic nucleophilic substitution,the coupling of carbanipns with aromatic halides.However,the reaction conditions were severe and harsh for the above conventional methods.Compared with the traditional synthetic methods,many groups utilized efficient cross-dehydrogenative coupling(CDC)to synthesize C1-benzoyl isoquinolines in recent years,aiming at generating C-C bonds directly from two different C-H bonds under oxidative conditions.Nevertheless,oxidizing substances were essential for the occurrence of the CDC reactions.Oxidizing agent was added to the reaction to bring out some unexpected byproducts probably,which was disadvantageous on the universality and yield of the reaction.Therefore,it is necessary to explore a novel and efficient method for composing C1-benzoyl isoquinolines.Hence,we revealed a facile synthesis of C1-benzoyl isoquinoline via Pd(?)-catalyzed intermolecular oxidative coupling reaction of isoquinoline N-Oxides with aromatic nitro alkenes.This domino process proceeds through C-H bond activation/intramolecular Michael addition to construct C1-benzoyl isoquinolines.(3)The bifunctional reaction of alkenes has become one of the important tools in organic synthesis,which offers many methods to synthesize important organic intermediates.Bifunctional research of unsaturated carbon-carbon bond has always been one of the hot areas.However,in order to achieve alkenes bifunctionalized many reactions require expensive metal or metal complexes as catalysts,or high-temperature heating or strong oxidants or other more severe conditions.Therefore,how to take advantage of inexpensive catalyst under mild conditions to achieve alkenes bifunctionalized has always been a challenge.We utilize inexpensive non-metallic NFSI as a catalyst to achieve alkenes bifunctionalized to construct selenium compounds.In addition,this method has the efficient,high yield,high selectivity,mild conditions advantages.