Facile Aldol Reaction Between Unmodified Aldehydes and Ketones in Bronsted Acid Ionic Liquids

A series of condensation reactions of unmodified ketones and aromatic aldehydes to prepare α,β-unsaturated carbonyl compounds by means of Aldol reactions in Bronsted acid ionic liquids（BAILs）was explored.1-Butyl-3-methylimidazolium hydrogen sulphate（BMImHSO4）acting as an effective media and catalyst in aldol reactions was compared with other BAILs,with the advantages of high conversion and selectivity.The product was easily isolated and the left ionic liquid can be readily recovered and reused at least 3 times with almost the same efficiency.The scope and limitation of the present method were explored and the possible catalytic mechanism was speculated.

Enantioselective Aldol Reactions of Aliphatic Aldehydes with Singh’s Catalyst

Aldols from aliphatic aldehydes had been synthesized enantioselectively using Singh’s catalyst. Self and crossed aldol reactions with several linear aldehydes were performed.

DFT Study on the (S)-Proline-catalyzed Direct Aldol Reaction between Acetone and 4-Nitrobenzaldehyde

DFT/6-31G^＊ calculations were applied to study the direct aldol reaction between acetone and 4-nitrobenzaldehyde catalyzed by （S）-proline. Four transition states associated with the stereo-controlling step, corresponding to syn and anti arrangements of methylene moiety related to the carboxylic acid group in enamine intermediate and re and si attacks to the aldehyde carbonyl carbon have been obtained. The solvent effect of DMSO was investigated with polarized continuum model. The computed energies of transition states reveal the stereo-selectivity of the reaction.

Direct asymmetric aldol reaction using MBHA resin-supported peptide containing L-proline unit

MBHA resin-supported tripeptide catalyst system containing L-proline unit has been developed for use in the direct asymmetric aldol reaction of acetone and aldehydes, which afford the corresponding products with satisfactory isolated yields and enantiomeric excesses. 2009 Hong Bin Zou. Published by E]sevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Mukaiyama Aldol Reaction of 1,2-Bis(trimethylsiloxy) Cyclobutene Catalyzed by Magnesium(II) Iodide

Efficient Mukaiyama-type aldol reaction of 1, 2-bis(trimethylsiloxy)cyclobutene with aromatic aldehydes catalyzed by MgI2 is reported. The resulting succinoylation product of aldehyde was converted into the synthetic useful g-lactone and butenolide derivatives.

Proline-based Amino Pyridine Dipeptides as Efficient Organocatalysts for Direct Aldol Reaction

A series of proline-based amino pyridine dipeptide organocatalysts was synthesized and applied in direct asymmetric intermolecular aldol reaction. These catalysts showed good solubility in organic solvents, good yields （73%--97%） and enantioselectivitives（74%--94%）. Among them, dipeptide organocatalyst（2） was found to be the most efficient one for the asymmetric aldol reaction between cyclohexanone and 4-nitrobeznaldehyde. After optimizing the catalytic reaction conditions, we found that the catalyst showed high yield（97%）, enantioselectivity（e.e., up to 92%） and anti-diastcreoselectivity（up to 95：5） at mild room temperature without any additives.

Novel Phenomenon of Oxygen-to-oxygen Silyl Migration in Directed Aldol Reaction

The phenomenon of migration of the silyl groups from α-oxygen to β-oxygen in sodium aldol reaction was observed for the first time in this paper.

Chiral Diamine-catalyzed Asymmetric Aldol Reaction

A highly efficient catalytic system composed of a simple and commercially available chiral primary diamine（1R,2R）-cyclohexane-1,2-diamine（6） and trifluoroacetic acid（TFA） was employed for asymmetric Aldol reaction in i-PrOH at room temperature.A loading of 10%（molar fraction） catalyst 6 with TFA as a cocatalyst could catalyze the Aldol reactions of various ketones or aldehydes with a series of aromatic aldehydes,furnishing Aldol products in moderate to high yields（up to 99%） with enantioselectivities of up to 99% and diastereoselectivities of up to 99：1.

Stereoselective synthesis of vic-halohydrins and an unusual Knoevenagel product from an organocatalyzed aldol reaction:A non-enamine mode

Stereoselective synthesis by an aldol reaction between chloroacetone and aldehyde was studied using a synthesized chiral organocatalyst and triethylamine. The reaction gave α-chloro-β-hydroxy ketones in excellent yield with high anti selectivity and enantioselectivity. The chiral organocatalyst was also used in the Knoevenagel reaction, which gave α-cyano-β-hydroxy ketones at a low temperature and the usual Knoevenagel product at a high temperature. Both products were obtained in good to moderate yield with good anti selectivity in the case of α-cyano-β-hydroxy ketone derivatives.

Recyclable Cyclohexanediamine Derivatives as Organocatalysts: Organocatalytic Reduction with Trichlorosilane and Aldol Reaction

Reduction of ketimine with trichlorosilane was carried out using bisformamide catalyst 1a derived from cyclohexanediamine to give the corresponding product in 81% yield with 39% ee. Deprotection of the formyl groups of the catalysts 1 gave the corresponding diamines 2 which were utilized in aldol reaction of acetone with 4-nitrobenzaldehyde. The reaction using 2b in brine afforded the aldol adduct in 81% yield with 29% ee.

Enantioselective Aldol Reactions and Michael Additions Using Proline Derivatives as Organocatalysts

Six compounds including five proline derivatives have been prepared and tested as chiral organocatalysts for enantioselective aldol reactions and Michael additions. The enantiomeric excesses, which are highly dependent on the molecular structure of catalysts as well as experimental conditions, have reached over 98%.

Stereoselective Synthesis of <i>cis</i>-Substituted-3’-anilino-2’, 3’-dihydro-4-2’-benzo[<i>b</i>]furanylcoumarins via Intramolecular Aldol Reactions

The present study reports the reaction of 4-bromomethylcoumarins with salicylidineaniline in acetone with two equivalents of potassium carbonate resulted in the formation of title compounds at room temperature via intramolecular aldolization. The obtained compound is thermodynamically and kinetically stable with highly stereoselective and excellent yield.

Stereoselective Aldol Reaction in Aqueous Solution Using Prolinamido-Glycosides as Water-Compatible Organocatalyst

Prolinamido-glycoside catalyzed asymmetric aldol reaction in aqueous media is reported. The reactions are rapid and highly stereoselective when water is used as solvent. The stereoselectivities were under influence of configurations of a prolyl residue of the catalyst and α-chiral aldehydes. Water soluble prolinamido-glycoside catalysts are easily separable from reaction mixture and can be recycled and re-used several times.

基于反应可逆性特点深化Aldol反应学习的方法及案例

Aldol反应是基础有机化学课程中的一个重点和难点内容。在教学实践中我们发现,通过一些基于Aldol反应可逆性原理的知识讲解和机理题目训练,能有效加深学生对Aldol反应的理解和认识,提升教学效果。本文我们分享了三个典型的基于可逆Aldol的重排反应案例,供各位教师和学生在教学和学习中作为参考。

Enzymatic Promiscuity： Escherichia coli BioH Esterase-catalysed Aldol Reaction and Knoevenagel Reaction

Esterase BioH,which is obligatory for biotin synthesis in Escherichia coli,was found to exhibit a promiscuous ability to catalyse Aldol and Knoevenagel reactions with moderate to good yields.The reaction conditions including organic solvent,molar ratio of ketone to aldehyde,enzyme amount,and reaction time were investigated to evaluate the effect of different reaction conditions on yield.Target compounds were afforded in the best yield of 91.2％ for Aldol reaction and 54.7％ for Knoevenagel reaction.In addition,because the enzyme could be prepared with a low cost,this protocol could provide an economic route to conduct Aldol and Knoevenagel reactions,which expand the field of enzymatic promiscuity.

Biocatalytic direct asymmetric aldol reaction using proteinase from Aspergillus melleus

The direct asymmetric aldol reaction of aromatic aldehydes with cyclic or acyclic ketones was catalyzed by proteinase from Aspergillus melleus (AMP) in acetonitrile in the presence of water. A wide range of substrates could be transformed into the corresponding aldol products in yields up to 89%, enantioselectivities up to 91% ee and diastereoselectivities up to >99:1 (anti/syn). This work provided an example of enzyme catalytic promiscuity that widens the applicability of this biocatalyst in organic synthesis without the need for additional cofactors or special equipment.

A high-performance potassium-ion capacitor based on a porous carbon cathode originated from the Aldol reaction product

Potassium-ion capacitors(KICs) emerge as a promising substitute for the well-developed lithium-ion capacitors(LICs),however,the energy density of KICs is below expectations because of lacking a suitable electrical double-layer positive electrode.Using chemical activation of the Aldol reaction product of acetone with KOH,we synthesized a porous ca rbon with a Brunauer-Emmett-Teller surface area of up to 2947 m2/g and a narrow pore size distribution ranging from 1 nm to 3 nm.Half-cell(versus potassium metal) test demonstrates that this porous carbon has high capacitive performance in K+ based organic electrolytes.Furthermore,a novel KIC fabricated by this porous carbon as the cathode,yields high values of energy density and power density.The processes used to make this porous carbon are readily low-cost to fabricate metal-ion capacitors.

Enzyme-catalyzed asymmetric domino aza-Michael/aldol reaction for the synthesis of 1,2-dihydroquinolines using pepsin from porcine gastric mucosa

An unprecedented enzyme-catalyzed asymmetric domino aza-Michael/aldol reaction of 2-aminobenzaldehyde and a,b-unsaturated aldehydes is achieved. Pepsin from porcine gastric mucosa provided mild and efficient access to diverse substituted 1,2-dihydroquinolines in yields of 38%–97% with 6%–24%enantiomeric excess（ee）. This work not only provides a novel method for the synthesis of dihydroquinoline derivatives, but also promotes the development of enzyme catalytic promiscuity.