Concerning the Solvent Effect in the Aldol Condensation

 Except for the catalyst and the temperature, the nature of the solvent also affects the aldol condensation, favouring α,β-unsaturated carbonyl compounds in alcoholic solvents or β-hydroxyl carbonyl compounds in tetrahydrofuran.     

Concerning the Solvent Effect in the Aldol Condensation

Summary.  Except for the catalyst and the temperature, the nature of the solvent also affects the aldol condensation, favouring α,β-unsaturated carbonyl compounds in alcoholic solvents or β-hydroxyl carbonyl compounds in tetrahydrofuran. Received November 22, 1999. Accepted (revised) December 21, 1999     

氧化铝催化双子丙酮缩合反应的机理

为了研究2,15－十六烷二酮在氧化铝表面的环合机理,选择小分子丙酮为模型化合物,用量子化学半经验AM1方法研究双分子丙酮在氧化铝表面的醛醇缩合机理,给出了反应过程中的5个过渡态和4个中间体的结构和几何参数,该催化反应可以认为是氧化铝分子与两分子丙酮分子发生静电络合作用,然后借助氧原子的负电荷导致脱氢并实现缩合,根据中间体的能量变化,推测有较稳定的铝复合物生成。     

ZrCl4 as an Efficient Catalyst for Crossed‐Aldol Condensation of Cyclic Ketones with Aromatic Aldehydes in Refluxing Ethanol

The aldol condensation reaction of cyclic ketones with aromatic aldehydes in ethanol under reflux conditions using ZrCl₄ as a catalyst to afford the corresponding α,α′‐bis(substituted benzylidene and cinnamylidene)cycloalkanones in excellent yields has been described. No self‐condensation product was produced.     

The Michael-Aldol Condensation Approach to the Construction of Key Intermediates in the Synthesis of Nimbolide and Nagilactone A

A short route for the preparation of highly oxygenated trans-decalines, key intermediates for the synthesis of nimbolide (2a) and nagilactone A (13), by a sequence involving a Michael addition followed by an aldol condensation, is described.     

A Simple Access to Chalcones via Modified Mukaiyama Aldol Condensation Promoted by SmI3／TMSCI

Promoted by SmI3,acetophenones and benzaldehydes can undergo the Mukaiyama type aldol condensation in the presence of TMSCl to form chalcones in good yields.     

Metal- and Solvent-Free Transesterification and Aldol Condensation Reactions by a Homogenous Recyclable Basic Ionic Liquid Based on the 1,3,5-Triazine Framework

A new recyclable basic ionic liquid was introduced as an efficient catalyst for aldol condensation and transesterification reactions under environmentally friendly conditions. The catalyst was prepared based on methyl imidazolium moieties bearing hydroxide counter anions via the Hofmann elimination on a 1,3,5-triazine framework. The ionic liquid with two functionalities including anion stabilizer and high basicity, was used as an efficient catalyst for aldol condensation as well as transesterification reaction of a variety of alkyl benzoates. All reactions were performed in the absence of any external reagent, co-catalyst, or solvent, in line with environmental protection. The kinetics isotope effect (KIE) was conducted for the transesterification reaction to elucidate the mechanism and rate determining step (RDS). It worth noted that, the homogeneous catalyst could be recycled from the reaction mixture and reused for several consecutive runs with insignificant drop of basicity and conversion.     

On Regioselectivity of Aldol Condensation of Aromatic Aldehydes with Borate Complex of Acetylacetone

While cinnamoyl acetone 1 is obtained in good yield by a condensation of 3 molar excess of a borate complex of acetylacetone with benzaldehyde, products of Knoevenagel condensation 2 are predominantly obtained with furfural and 5-substituted furfurals. Cinnamoyl acetone 1 can be further condensed with furfural to form unsymmetrical curcuminoid 5. Compound 2a does not produce any new products under the same conditions. Compounds 3 and 5 are good inhibitors of growth of protozoan Trichomonas vaginalis.     

Organocatalytic Atroposelective Aldol Condensation: Synthesis of Axially Chiral Biaryls by Arene Formation

Axially chiral compounds are of significant importance in modern synthetic chemistry and particularly valuable in drug discovery and development. Nonetheless, current approaches for the preparation of pure atropisomers often prove tedious. We demonstrate here a synthetic method that efficiently transfers the stereochemical information of a secondary amine organocatalyst into the axial chirality of tri‐ortho‐substituted biaryls. An aromatic ring is formed during the dehydration step of the described aldol condensation cascade, leading to highly enantioenriched binaphthyl derivatives. The fundamental course of the reaction is related to the biosynthesis of aromatic polyketides.     

On the Diastereoselectivity of the Aqueous-Acid-Catalyzed Intramolecular Aldol Condensation of 3-Oxocyclohexaneacetaldehydes

The factors responsible for the diastereoselective formation of the 6-endo-hydroxybicyclo[2.2.2]octan-2-one by acid-catalyzed intramolecular aldol reaction of 3-oxocyclohexaneacetaldehydes have been investigated. This study, carried out on (1SR,4RS,6RS)-6-hydroxybicyclo[2.2.2]octan-2-one 1a , (1SR,4RS,6SR)-6-hydroxybicyclo[2.2.2]octan-2-one 1b , and 3,3-(ethylenedioxy)cyclohexaneacetaldehyde 2a , allowed to demonstrate the absence of intramolecular H-bonding in 1a as a stabilizing factor, and to ascertain the presence of unfavorable steric interactions in 1b .     

Fluorinated Retinoids via Crossed Aldol Condensation of 1,1,1-Trifluoroacetone

Piperidine-acetic acid catalysed crossed aldol condensation of 1,1,1-trifluoroacetone with aryl or α,β-unsaturated aldehydes was found to be a useful method for the preparation of unsaturated trifluoromethyl ketones. Chain extension of these ketones led to several new fluorinated retinoids including the hitherto elusive all-trans isomers of 19,19,19- and 20,20,20-trifluororetinal.     

Aldol Condensation for the Construction of Organic Functional Materials

Aldol condensation is a cost-effective and sustainable synthetic method, offering the advantages of low complexity, substrate universality, and high efficiency. Over the past decade, it has become popular for creating next-generation organic functional materials, particularly rigid-rod conjugated (semi)conductors. This review focuses on conjugated small molecules, oligomers, and polymeric (semi)conductors synthesized through aldol condensation, with emphasis on their remarkable features in advancing n-type organic field-effect transistors (OFETs), organic electrochemical transistors (OECTs), organic photovoltaics (OPVs), and organic thermoelectrics (OTEs) as well as NIR-II photothermal conversion. Coherence character, optical properties, microstructure, and chain conformation are investigated to understand material-property relationships. Future applications and challenges in this area are also discussed.     

2D Poly(arylene vinylene) Covalent Organic Frameworks via Aldol Condensation of Trimethyltriazine

Designing structural order in electronically active organic solids remains a great challenge in the field of materials chemistry. Now, 2D poly(arylene vinylene)s prepared as highly crystalline covalent organic frameworks (COFs) by base‐catalyzed aldol condensation of trimethyltriazine with aromatic dialdehydes are reported. The synthesized polymers are highly emissive (quantum yield of up to 50 %), as commonly observed in their 1D analogues poly(phenylene vinylene)s. The inherent well‐defined porosity (surface area ca. 1000 m² g^?1, pore diameter ca. 11 Å for the terephthaldehyde derived COF‐1) and 2D structure of these COFs also present a new set of properties and are likely responsible for the emission color, which is sensitive to the environment. COF‐1 is highly hydrophilic and reveals a dramatic macroscopic structural reorganization that has not been previously observed in framework materials.     

Mutual Kinetic Resolution in Aldol Condensation between 2-Phenylpropanal and 4,5-Dihydro-5-methyl-2-(trimethylsiloxy)-3-(trimethylsilyl)furan

The titanium(IV) chloride-mediated aldol condensation between title compounds proceeds with high diastereoselectivity (Cram) to give $\text{3a}$ exclusively (99% purity).     

A Versatile Approach for Synthesis of 2,3-Dimethyl Chroman-4-ones,Intermediate for Calanolide Anti-HIV Agents,VIA Aldol/Mitsunobu Reactions

Combined aldol/Mitsunobu reactions have been employed for the first time for synthesis of 2,3-dimethyl chroman-4-ones, intermediates for calanolide anti-HIV agents. Thus, the lithium enolate of chromene 1 reacted with acetaldehyde at -78°C to afford the aldol products 4 and 5. Under Mitsunobu conditions (Ph₃P/DEAD), the syn aldol product 4 led to the formation of trans-2,3-dimethyl chroman-4-one 2 while the anti aldol product 5 yielded both trans and cis derivatives (2 and 3). The use of other phosphorous and azo compounds in this reaction has also been investigated.     

Facile and Convenient Synthesis of 5-Arylalkylidenerhodanines by Electrocatalytic Crossed Aldol Condensation

Abstract

An electrochemically induced catalytic crossed Aldol condensation of one equivalent of rhodanine with various aromatic aldehydes and ketones in ethanol in an undivided cell in the presence of sodium bromide as an electrolyte results in the formation of the corresponding 5-arylalkylidenerhodanines in 80–96% yield with reactions in 40 min.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Formation of Dimers of Some 2‐Substituted Indan‐1‐one Derivatives during Base‐Mediated Cross‐Aldol Condensation

Unexpected dimers of some 2‐substituted indan‐1‐one derivatives were isolated during aldol condensation of indan‐1‐one with various aldehydes in the presence of KOH (see Scheme). Monomeric products, usually expected from aldol condensation, further underwent a base‐catalyzed nucleophilic addition reaction to their dimeric form in some cases. The structures of these dimers were characterized by using various spectral techniques and in one case, structural details were determined from a high‐resolution crystallographic analysis.     

Versatile One‐Step One‐Pot Direct Aldol Condensation Promoted by MgI2

A true one‐step one‐pot aldol‐reaction procedure has been developed for the synthesis of β‐hydroxy ketones and esters. The reaction can be run at room temperature by simply mixing four components in CH₂Cl₂, with medium‐to‐high yields of aldol products obtained after regular workup. Mechanistically, the process probably proceeds via Mg‐enolate formation of the ketone or ester component, followed by addition to the electrophilic aldehyde.     

Functioned Calix[4]arenes as Artificial Enzymes Catalyze Aldol Condensation

Aldolcondensationcanbegenerallycatalyzedbymeansofbasesoracids.Usually,itiseasytoobtainα,β-unsaturatedketonesderivedfromthedehydrationofthealdol-typeproducts(β-hydroxyketones).Watanabeetal'successfullydevelopedthemethodtodepressthedehydrationbyusingmetal(Ⅱ)complexesofα-aminoacidesterswithcyclodextrin.Later,ZhaoHua-mingetal.2．3studiedthefunctionedcyclodextrinsasaldolasetomimicthecondensationofp-nitrobenzaldehydewithacetoneandobtainedtheaIdol-typeproductingoodyield.Recentyears,studiesonca…     

One-Pot Lipase-Catalyzed Aldol Reaction Combination of In Situ Formed Acetaldehyde

A facile tandem route to α,β-unsaturated aldehydes was developed by combining the two catalytic activities of the same enzyme in a one-pot strategy for the aldol reaction and in situ generation of acetaldehyde. Lipase from Mucor miehei was found to have conventional and promiscuous catalytic activities for the hydrolysis of vinyl acetate and aldol condensation with in situ formed acetaldehyde. The first reaction continuously provided material for the second reaction, which effectively reduced the volatilization loss, oxidation, and polymerization of acetaldehyde, as well as avoided a negative effect on the enzyme of excessive amounts of acetaldehyde. After optimizing the process, several substrates participated in the reaction and provided the target products in moderate to high yields using this single lipase-catalyzed one-pot biotransformation.