二烯酮类化合物在构建复杂有机化合物中的应用  

Application of dienones in the construction of complex organic compounds

作　　者：曹海泳 刘文琴[1] 万屏南[1] 林艳[1] 崔汉峰[1] CAO Haiyong;LIU Wenqin;WAN Pingnan;LIN Yan;CUI Hanfeng(College of Pharmacy,Jiangxi University of Traditional Chinese Medicine,Nanchang 330004,Jiangxi,China)

机构地区：[1]江西中医药大学药学院,江西南昌330004

出　　处：《精细化工》2020年第8期1540-1552,共13页Fine Chemicals

基　　金：国家自然科学基金(81560625);江西省教育厅科技项目(GJJ160829,GJJ190668)。

摘　　要：二烯酮作为一类具有多个化学反应位点的不饱和酮类化合物,可与多种反应底物实现不同类型的化学转化,高效快捷地构建功能各异的有机化合物。该文综述了近些年二烯酮类化合物与多种反应底物的化学转化。首先,探讨了2,5-环己烯酮类化合物与不同试剂的串联Michael-Smiles环丙烷化反应、环加成反应、三组分Ritter反应、光化学重排反应和氧化偶联反应分别构建了环丙烷类衍生物、氮杂螺环类衍生物、含氟烷基N,O-缩酮类衍生物、稠环吲哚类化合物、酰胺类化合物和不对称联芳烃类化合物。接着,分析了1,4-戊二烯-3-酮类化合物与丙二腈(硝基甲烷)、硫氢化钠、氧化吲哚、吡唑酮、芴和巴比妥酸双Michael加成反应,分别合成了多取代环己酮类化合物、二芳基噻喃酮类化合物、螺环氧化吲哚类化合物、螺环吡唑酮类化合物、螺环芴类化合物和螺环巴比妥类衍生物。然后,介绍了2,4-戊二烯-1-酮类化合物的1,4-共轭加成、氮杂Michael加成反应、分子内Morita-Baylis-Hillman(MBH)反应、分子内还原Aldol反应、分子内Aldol反应和分子内[4+2]环加成/氧化反应分别实现了有机含硫化合物、有机含氮化合物、多取代茚酮类化合物和SGLT2抑制剂——托格列净关键中间体的制备。最后,对二烯酮在后续化学反应中的潜在应用进行了展望。Dienones,a kind of unsaturated ketones with multiple chemical reaction sites,can achieve different types of chemical conversion with a variety of substrates,and construct organic compounds with different functions efficiently.The chemical transformation of dienones with different substrates in recent years is reviewed.Firstly,a series of tandem Michael-Smiles cyclopropanation reaction,cycloaddition reaction,three-component Ritter reaction,photoinduced rearrangement reaction and direct oxidative coupling reaction between cyclohexa-2,5-dienone compounds and different reagents were discussed.These reactions construct aze heterocyclic derivatives cyclopropane derivatives,aze heterocycllc dervatives fluoroalkylated N,O-ketal derivatives,ring-fused indoles,amides and unsymmetrical biaryls,respectively.Subsequently,double Michael additions of 1,4-pentadien-3-one derivative with malononitrile(nitromethane),sodium hydrosulfide,oxindole,pyrazolone,fluorene and barbituric acid were analyzed,and the corresponding reactions obtained multi-substituted cyclohexanones,diaryltetrahydrothiopyran-4-ones,spirocyclic oxindoles,spirocyclic pyrazolones,spirofluorenes and spirobarbituric acid derivatives.Then,1,4-conjugate addition,Aza-Michael addition,intramolecular Morita-Baylis-Hillman(MBH)reaction,intramolecular reductive Aldol reaction,intramolecular Aldol reaction and intramolecular[4+2]cycloaddition reaction of 2,4-pentadien-1-one compounds are introduced,which realize the preparation of organic sulfur compounds,organic nitrogen compounds,multi-substituted indanones and key intermediate of SGLT2 inhibitor Tofogliflozin.Finally,the potential application of dienones in the subsequent chemical reactions is prospected.

关 键 词：二烯酮 2 5-环己烯酮 1 4-戊二烯-3-酮 2 4-戊二烯-1-酮 有机合成 复杂有机化合物 

分 类 号：O625.4[理学—有机化学]