离子液体中二羰基化合物的烷基化反应

为取代传统的有机溶剂，离子液体将为现代化学溶剂提供一种新颖而环境友好的选择，以1－丁基吡啶四氟硼酸盐为离子液体，实现了1，3－二羰基化合物的烷基化反应，提供了一种既方便又实用的操作方法。     

Fluorocontaining 1,3-Dicarbonyl Compounds in the Synthesis of Pyrimidine Derivatives

Hexafluoroacetylacetone reacts with urea (thiourea) to yield respectively 4,6-bis(hydroxy)-4,6-bis(trifluoromethyl)hexahydropyrimidin-2-one(thione). The dehydration of the products and also reaction of nonsymmetrical fluoroalkyl-containing 1,3-diketones with urea (thiourea) afford substituted pyrimidines. The condensation of fluorinated 3-oxoesters and 1,3-diketones with benzaldehyde and urea (thiourea) results in 5-alkoxycarbonyl(acyl)-4-hydroxy-2-oxo(thioxo)-6-phenyl-4-fluoroalkylhexahydropyrimidines that on dehydration furnish 5-alkoxycarbonyl(acyl)-2-oxo(thioxo)-4-phenyl-6-fluoroalkyltetrahydropyrimidines. Ethyl 7-nonafluorobutyl-5-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidine-6-carboxylate hydrobromide forms in reaction of dibromoethane with ethyl ether of 2-thioxo-4-phenyl-6-nonafluorobutyltetrahydropyrimidine.     

Copper(II) Triflate Catalyzed Amination of 1,3-Dicarbonyl Compounds

A method to prepare α,α-acyl amino acid derivatives efficiently by Cu(OTf)(2) +1,10-phenanthroline (1,10-phen)-catalyzed amination of 1,3-dicarbonyl compounds with PhI?NSO(2) Ar is described. The mechanism is thought to initially involve aziridination of the enolic form of the substrate, formed in situ through coordination to the Lewis acidic metal catalyst, by the putative copper-nitrene/imido species generated from the reaction of the metal catalyst with the iminoiodane source. Subsequent ring opening of the resultant aziridinol adduct under the Lewis acidic conditions then provided the α-aminated product. The utility of this method was exemplified by the enantioselective synthesis of a precursor of 3-styryl-2-benzoyl-L-alanine.     

Cyclohexenones Through Regioselective Addition of 1,3-Dicarbonyl Compounds to Terpenoid-Like Bischalcones

Terpenoid-like bischalcones (3 and 4) were synthesized from the reaction of α- and β-ionones and benzaldehydes in excellent yields. The Michael addition of 1,3-dicarbonyl compounds to bischalcones (3 and 4) resulted in the formation of cyclohexenones derivatives (10a–d and 14a, b) via regioselective addition of 1,3-dicarbonyls and then cyclization.     

Cerium Catalyzed Michael Addition of 1,3-Dicarbonyl Compounds Under Microwave Irradiation

Cerium chloride heptahydrate proves to be an efficient catalyst for Michael addition of 1,3-dicarbonyl compounds, through a simple solvent free reaction under microwave irradiations.     

Oxidative Coupling of 1,3-Dicarbonyl Compounds by Cerium(IV) Ammonium Nitrate

A fast, mild, and highly efficient method for the intermolecular coupling of 1,3-dicarbonyl compounds using cerium ammonium nitrate in CH₃CN/CH₃OH/H₂O has been described. The procedure provided a convenient method for the synthesis of 1,4-diketone derivatives with excellent yields (up to 96%) and powerful evidence for the oxidation mechanism mediated by cerium ammonium nitrate.     

A Convenient and Improved Procedure for the Cyanation of Enamines and 1,3-Dicarbonyl Compounds

The direct cyanation of enamines 2a-f using acylsubstituted cyanatobenzenes 1a-c and cyanatoanthraquinone 1d furnishes β-cyanoenamines 3a-f which upon hydrolysis afford the cyanoketones 4a,b. 2-Cyano-1,3-diketones 6a-c are obtained starting from compounds 5a-c and 1.     

Palladium-Catalyzed Synthesis of 3-Alkylphthalides via Carbonylative Cyclization of o-Bromobenzaldehyde with 1,3-Dicarbonyl Compounds

o-Bromobenzaldehyde reacts with 1,3-dicarbonyl compounds under carbon monoxide in the presence of a catalytic amount of PdCl₂(PPh₃)₂ to give the corresponding 3-alkylphthalides in moderate to good yields.     

A Facile P-C Bond Cleavage of 2-Fluoro-2-Phosphonyl-1,3-Dicarbonyl Compounds on Silica Gel

α-Fluoro-β-keto esters and α-fluoromalonates were prepared by the P-C bond cleavage of 2-fluoro-2-phosphonyl-1,3-dicarbonyl compounds on wet silica gel.     

Ring-Chain Tautomerism of 1,2,3,4-Tetrahydroquinazolines. The Products of Reaction of 1,3-Dicarbonyl Compounds with 2-Aminomethylaniline

The reaction of 2-aminomethylaniline with 1,3-dicarbonyl compounds gives a series of 1,2,3,4-tetrahydroquinazoline derivatives. A ring-chain tautomeric equilibrium of the type enamine-1,2,3,4-tetrahydroquinazoline is observed in solutions of these compounds and its position depends of the structure of the starting dicarbonyl component and the solvent polarity.     

Studies on Retro-Michael Reaction of 1,5-Dicarbonyl Compounds

MethylatedtricyclicterPanesareAnpohaIlnovelbiomarkerSrecentlydiscoveredfrOmabogheadsampleinShuicheng,weStemGudriouofChina'.InconnectionwithoursynthesisofthisseriesofmethylatedtricyclicteIPanes,thedeMichaelreachonofl,5-dicarbonylcomPOundsderivedfrOmcholestaneordaIIunaraneisProectedtobeemployedasakeystep.LiteratUrsearchshowsthatthisreactionwodswellforaromallcl,5-dthetonesintheinletofmasssPectrometer2.Foralicyclicketones"',however,boicconditionsareneededandleadtopoorormoderateyields.Recen…     

Furan Derivatives from Cyclodehydratign of Brackein-Like 1,4-Dicarbonyl Compounds

The synthesis of 2,3,4,5 tetrasubstituted and 2,3,5-trisubstituted furans from suitable butan-1,4-dione derivatives is described.     

β—二羰基化合物的电解氧化偶联反应

β┐二羰基化合物的电解氧化偶联反应朱洪友张成敏刘复初＊（云南大学化学系昆明６５００９１）关键词β－二羰基化合物，电氧化，偶联反应１９９７－０６－０４收稿，１９９７－１２－１０修回云南省应用基础研究基金资助项目在有机合成上，β－二羰基化合物的偶联是形成...     

1,3-Dicarbonyl compounds in stereoselective domino and multicomponent reactions

Modern organic synthesis focuses on the discovery and the development of stereoselective multiple bond-forming transformations allowing the creation of several covalent bonds in a single operation. Hence, the number of steps required to obtain a target molecule is reduced, which nicely addresses the efficiency and economy criteria of ‘green chemistry’. In this context, 1,3-dicarbonyl compounds are exceptional synthetic platforms due to the presence of four contiguous reaction sites. This functional group density allows cascades of elemental steps from simple substrates leading to the selective formation of elaborated molecular architectures displaying a large functional diversity.     

缩杂环酮化合物的合成

酮(troponoid)是自然界中某些抗菌素和毒菌的基本骨架组成。近年来,人们合成了许多具有各种生理活性的酮类化合物,而     

Synthesis of Spiroannulated Dihydrofurans by Cerium(IV) Ammonium Nitrate Mediated Addition Of 1,3-Dicarbonyl Compounds to Exocyclic Alkenes

Cerium (IV) ammonium nitrate (CAN) mediated addition of 1, 3-dicarbonyl compounds to exocyclic alkenes occurs smoothly at 5°C in methanol to afford spiroannulated dihydrofurans in moderate to good yields.     

Reformatsky Reaction of Methyl 1-Bromocycloalkanecarboxylates with α-Dicarbonyl Compounds

Reformatsky reactions of methyl 1-bromocyclohexanecarboxylate and methyl 1-bromocyclo-pentanecarboxylate with 2-aryl-2-oxoacetaldehydes involve both carbonyl groups of the latter and result in formation of 3a-aryl-3,3 : 6,6-bis(pentamethylene)- and 3a-aryl-3,3 : 6,6-bis(tetramethylene)tetrahydrofuro-[3,2-b]furan-2,5-diones. The reaction with 2-(2,4-dimethylphenyl)-2-oxoacetaldehyde gives acyclic products, methyl 1-[1-hydroxy-2-(2,4-dimethylphenyl)-2-oxoethyl]cyclohexanecarboxylate and methyl 1-[1-hydroxy-2-(2,4-dimethylphenyl)-2-oxoethyl]cyclopentanecarboxylate, while with benzil methyl 1-(4-hydroxy-1-oxo-3,4-diphenyl-2-oxaspiro[4.5]dec-3-yl)cyclohexanecarboxylate and methyl 1-(4-hydroxy-1-oxo-3,4-diphenyl-2-oxaspiro[4.4]non-3-yl)cyclopentanecarboxylate are obtained.