Discovery And Biomimetic Synthesis Of Natural Diarylpropanes

Diarylpropane is also called reduced chalcone,which is less distributed in nature.So far,These compounds mainly exist in Horsfieldia of Myristicaceae,Combretum of Combreaceae and Euonymus of Celastraceae.In 2018,a series of novel 1,3-diarylpropane dimer compounds were found in Horsfieldia.tetratepala,which has raised our concern.Moreover,Horsfieldia.Tetratepala was absorbed into Horsfieldia kingii in 2019.In order to further understand the activity of diarylpropanes and find the active secondary metabolites,we once again analyzed the branches and leaves of Horsfieldia kingii collected from Xishuangbanna Prefecture.The chemical composition of the branches and leaves was studied.Meanwhile,the study of bio-inspired synthesis and anti-inflammation of three important natural diarylpropane compounds of horsfiequinone A,horsfielenides C and horsfielenides D are completed.by our group in the early stage.On the basis of understanding the reaction characteristics of diarylpropane,and at the same time lay the foundation for the subsequent further completion of the synthesis of diarylpropane dimers horisfieldones A and B.In the last chapter,the key cyclic carbonyl compound α-C(sp3)-H arylation reaction was reviewed.Thirty compounds are isolated and identified by column chromatography and spectral analysis.The compounds respectively are:(1),1-(2-hydroxy-4-methoxyphenyl)-3-(3,4-methylenedioxyphenyl)-ropan-2-ol(2),3-(4-methoxyphenyl)-2-hydroxy-1-(2-hydroxy-4-m ethoxyphenyl)-1-propanone(3),1-(2’-hydroxy-4’-methoxyphenyl)-propane-3-(4"-hydroxy-3"-methoxyphenyl)(4),1-(4’-hydroxy-2’-methoxyphenyl)-propane-3-(4"-hydroxy-3"-methoxyphenyl)(5),(2R)-4’,4,",6’-trihydroxy-2’,3"-dimethoxy-1,3-diarylpropan-2-ol(6),virolanol C(7),prunetin(8),5-hydroxyflavanone(9),pinocembrin(10),(2S)-7,3’-dimethoxy-4’-hydroxyflavan(11),7-hydroxyflavonone(12),biochanin A(13),formononetin(14),4’,7-dimethoxy-5-hydroxy-isoflavone(15),2’-hydroxyformononetin(16),irilin D(17),5,7,4’-trihydroxy-6,3’-dimethoxyisoflavone(18),tectorigenin(19),liquiritigenin(20),irilone(21),2’,5,7-trihydroxy-4’-metoxyisoflavone(22),4-acetonyl-3,5-dimethoxy-p-quinol(23),loloilide(24),isovanillic acid(25),2-methoxy-4-formylphenol(26),dehydrovomifoliol(27),methyl orsellinate(28),ferulyl aldehyde(29),β-sitosterol(30)。Compounds 2-3,5-12,15,17-21,23-29 are separated from this plant for the first time,and compounds 5-6,8-9,11,17,23-27,29 are obtained from this genus for the first time.In Chapter 2,the study of bio-inspired synthesis and anti-inflammation of three important natural diarylpropane compounds of horsfiequinone A,horsfielenides C and horsfielenides D are completed.Firstly,the bio-inspired synthesis and anti-inflammation in vitro of horsfiequinone A are studied.Inspired by the oxidation of the oxy-tyrosinase type Ⅱ copper enzyme,a key oxidation method of applying CuOTf/DBED/O2 is explored and found to achieve the biomimetic transformation of horsfiequinone A in 47%yield.It is proved that horsfiequinone A has good anti-inflammation in vitro by pharmacological and molecular docking experiments.Then,the study of bio-inspired synthesis and anti-inflammation in vitro of horsfielenides C and horsfielenides D is completed,and diarylpropane compounds are constructed from simple small molecules.The key Friedel-Crafts cyclization reaction is used to realize the bio-inspired synthesis of horsfielenides C and horsfielenides D in 28%and 36%yields,respectively.Meanwhile the anti-inflammation in vitro is studied.It is proved that horsfielenides C and horsfielenides D have good anti-inflammation in vitro by pharmacological experiments.The last chapter reviews the key Progress in α-C(sp3)-H Arylation of Cyclic Compounds with Carbonyl Groups,mainly including the review of α-C(sp3)-H arylation reaction of Cyclic Compounds with Carbonyl Groups covering cyclic ketones,lactones and lactams in recent 20 years.