The Synthesis Of Dihydroquinolinone And Indenone By Oxidative Decarbonylation Of Aliphatic Aldehydes

The structural units of dihydroquinolinone and indenone are widely found in natural products and drugs.And dihydroquinolone can also be used as an intermediate to convert into other compands.In the previous reports on the synthesis of the two structures,most of these methods have disadvantages such as the use of noble metal catalyst and preactivation of substrates.In order to find a more economical and effective synthesis method,We have proposed a method for oxidative decarbonylation of aliphatic aldehydes to obtain alkyl radicals,and radical addition cyclization of olefins or alkynes to form dihydroquinolinones and indenones.This disertation is mainly consist of the following two parts:The first part,We have developed a method for the synthesis of3,4-dihydroquinoline-2(1H)-ones derivatives using Fe(acac)3 as catalyst,DTBP as oxidant and radical initiator,cheap and readily available aliphatic aldehydes and N-arylcinnamamides as substrates.This method produces alkyl radicals of 1~o,2~o and3~o by oxidative decarbonylation of aliphatic aldehydes,and then the radical is added to the?position of N-arylcinnamamides to form benzylic radical,and then a HAS-type reaction with the aromatic ring occurs.The C(sp~3)-C(sp~3)and C(sp~3)-C(sp~2)bonds were constructed in one step.Thus,3,4-dihydroquinoline-2(1H)-ones derivatives with specific structure were synthesized.Compared with previous synthetic methods,The method uses environmentally benign iron catalyst and commercially available raw materials,avoiding the use of ligands and additives.A simple way to generate carbon radicals and this protocol has a wide range of functional group toluence.This method will be attractive enough in organic synthesis and pharmaceutical chemistry.The second part,We have developed a method for the synthesis of indenone derivatives using aliphatic aldehydes and aryl acetylene ketones as substrates.Through the previous part of the work and combined with the previous research work of our group,We used arylalkynones instead of N-arylcinnamamides by oxidative decarbonylation of aliphatic aldehydes to generate alkyl radicals and arylalkynones to undergo radical addition and cyclozation,the C(sp~3)-C(sp~2)and C(sp~2)-C(sp~2)bonds were constructed in one step,and the derivatives of indenone were synthesized.The raw materials of this synthesis method are cheap and easy to obtain without the involvement of transition metals.