Synthesis Of Thiophene[2,3-b] Indole Derivatives And Asymmetric Hydrogenation Of Quinoline Derivatives

Indole and its derivatives are widely found in natural products and biologically active drugs,among which thienoindene derivatives are one of the most important members.Because of their potential biological activity,they are widely used in agrochemistry and pharmaceutical industry.At present,there have been many reports on the synthesis of thienopyrene derivatives.Recent studies have found that thiophene derivatives are also widely used in the design of new electroluminescent materials for light emitting devices.At present,there are many reports on the synthesis of derivatives,but most of the current reports still have some shortcomings:First,the sulfur sources in thienopyridines mostly come from organic sulfur,compared with inorganic sulfur,organic sulfur is more expensive,has pungent odors,and is more complex to prepare;second,multi-step reactions are gradually separated,which not only greatly reduces efficiency,but also detrimental to atomic economy and environmental friendliness;third,most synthetic methods require transition metals.Participate in catalysis.In response to these scientific problems,combined with the research basis of this project group to use multi-component reactions to construct C-S bond compounds,this paper developed a method in which Bmsted acid catalyzes the use of elemental sulfur as the sulfur source,and the cesium,phenylacetylene,or styrene is high-yield synthesis of thieno[2,3-b]anthraquinone by one-pot method.The main research results obtained are as follows:1.Synthesis of three-component substituted thieno[2,3-b]anthraquinone starting from fluorene and alkene with elemental sulfur as the sulfur source.A new method for the synthesis of thieno[2,3-b]indoles without transition metals was developed through system optimization and investigation of reaction conditions(isolation yield up to 82%),of which N,N-dimethyl Formamide plays an important role in converting raw materials into products.The various functional groups of the substrate are well tolerated to provide the corresponding product in moderate to good yield under very simple reaction conditions.Therefore,this method provides a simple,gentle and efficient new route for the synthesis of thieno[2,3-b]anthracene and its derivatives.2.Using styrene and hydrazine as raw materials,a series of synthetic methods for the synthesis of thieno[2,3-b]indoles and their derivatives with simple conditions were developed.With the inexpensive elemental sulfur as the promoter,the reaction yield is good without transition metal participation.Based on this research,a class of derivatives of thieno[2,3-b]anthraquinone and its derivatives was realized through a one-pot method.It provides a new choice for the synthesis of heterocyclic compounds under the condition of no transition metal participation.3.The chiral diamine metal iridium complex catalyst was successfully applied to the asymmetric hydrogenation of aromatic heterocyclic 2,2'-methylene bisquinoline derivatives,and the substrate was developed under optimal reaction conditions.The series of substituted 2,2'-methylene bisquinoline derivatives can successfully achieve catalytic hydrogenation,The highest value of the hydrogenation reaction>20:1,ee values as high as 99%.The hydrogenated product is simply derivatized to obtain a chiral imidazolium salt derivative in high yield.As a chiral carbene precursor,We will apply it to asymmetric catalytic reactions.