Intramolecular Induction of Asymmetric Darzen's Condensation of Aldehydes with Chiral α-Chloroacetates

Inconvergentwithourinterestintheasymmetricsynthesisofnaturalproducts,intramolecularinductionofasymmetricDarzen'scondensationlofaldehydeswithQchloroacetatesofchiralalcoholswasstudies,asshowninScheme1.Scheme1.R*OH CICH,COCI~CICH,COOR*i(-)-menthol(450%)3( )-Jsomenthoi(i56%)5(-)-8-phenylmenthoi(74%)2( )-neomenthol(147%)4( )-f6nchol(478%)6(-)-8-11-naphthylmenthoi(99%)I-henumbersintileparenthesisilldicatedthece%oftilecorrcspondillgmethy13-pllcn}lgl}'cidatcobtainedh\'trallscstcrltiationBenza…     

Aldol Condensation of β-Diketones and β-Ketoesters with Aldehydes Catalyzed by Samarium (III) Iodide

Catalyzed by SmI₃ β-diketones and β-ketoesters condense with aldehydes to give benzylidene substituted β-diketones and β-ketoesters at room temperatures in fair yields.     

Condensation Reaction of α-Aroyl-α-acetyl Ketene Cyclic Dithioacetals with Aromatic Aldehydes

Asaversatilethree-carbonsynthon,a--oxoketenedimethylthioacetalsIhavebeenappliedinmanyfields'.Inourpreviousworks'-',someproperties,especiallyadditionselectivity,ofthearoxoketenecyclicdithioacetals2werefoundtobequitedifferentfromthoseof1.Herea--aroyl...     

InCl_3·4H_2O Catalyzed Aldol Condensation of Cycloalkanones with Aromatic Aldehydes

a, a-Bis (substituted) benzylidenecycloalkanones are widely used as precursors for synthesis of bioactive pyrimidine derivatives and their synthesis have attracted considerable attention1. Aldol condensation of cyclopentanone or cyclohexanone with aldehydes is employed, and the reactions were carried out in the presence of strong acids or bases2. Recently, the application of metal ions as catalyst in this type of reaction has been reported3. For example, RuCl3 has been reported to be an exc…     

Selective Hydrogenation of α,β-Unsaturated Aldehydes Catalyzed by Amine-Capped Platinum-Cobalt Nanocrystals

More Greasy, More Selective: Amine-capped Pt(3) Co nanocatalysts were synthesized and used for the hydrogenation of cinnamaldehyde (CAL). Capping the catalysts with amines that contain long carbon chains results in an ordered surface "array", in which high selectivity towards C?O hydrogenation can be achieved because the C?C bond in CAL does not interact with the surface. The longer the carbon chains in the amine, the higher the selectivity.     

Nickel-Catalyzed α-Allylation of Aldehydes and Tandem Aldol Condensation/Allylation Reaction with Allylic Alcohols

An additive-free nickel-catalyzed α-allylation of aldehydes with allyl alcohol is reported. The reaction is promoted by 1 mol % of in situ formed nickel complex in methanol, and water is the sole by-product of the reaction. The experimental conditions allow the conversion of various α-branched aldehydes and α,β-unsaturated aldehydes as nucleophiles. The same catalyst and reaction conditions enabled a tandem aldol condensation of aldehyde/α-allylation reaction.     

Microwave-Assisted Acetalization of Carbonyl Compounds Catalyzed by Reusable Envirocat® Supported Reagents

Envirocat® supported reagents (EPZG, EPZ10, and EPIC) are found to efficiently catalyze the acetalization of carbonyl compounds with 1,2-ethanediol under microwave irradiation under solvent-free conditions. The reagents can be used in repeated experiments to perform the reaction with the same activity.     

Synthesis of α,β-Unsaturated Nitriles from the Iodine Catalyzed Reaction of Chloroacetonitrile with Aldehydes Promoted by Tri-n-Butylarsine and Magnesium

α,β-Unsaturated nitriles were synthesized from the iodine catalyzed reaction of chloro-acetonitrile with aldehydes promoted by tri-n-butylarsine and magnesium.     

α-Amination of Aldehydes Catalyzed by In Situ Generated Hypoiodite

The metal-free amination of different aldehydes is catalyzed by hypoiodite, which is generated by employing commercially available sodium percarbonate as the co-oxidant. This approach has several advantages: it is a metal-free oxidation that works under mild reaction conditions; furthermore, it has a wide substrate scope and does not give toxic by-products from the co-oxidant that is used.     

Enantioselective Addition of Phenylacetylene to Aldehydes Catalyzed by Polymer-Supported Sulfonamide

Enantioselective formation of C-C bonds is an area of intense research. Among them, the asymmetric addition of alkynyl reagents to aldehydes is very useful for the synthesis of chiral secondary propargyl alcohols.[1] Recently, many significant homogeneous chiral ligands have been disclosed,[2,3] but very few efficient heterogeneous catalysts have been reported. Herein, we report our research results in the asymmetric addition of phenylacetylene to aldehydes catalyzed by polymer-supported chiral sulfonamide.     

The Condensation of Aromatic Aldehydes with Acidic Methylene Compounds in Water

The condensation of aromatic aldehydes with acidic methylene compounds such as malononitrile, methyl cyanoacetate, cyanoacetamide, 5,5-dimethyl-1,3-cyclohexanedione,bartbituric acid and 2-thiobarbituric acid proceeded very efficiently in water in the presence of triethylbenzylammonium chloride (TEBA) and the products were isolated simply by filtration.     

Efficient Synthesis of Dicycloalkenopyridines： One-pot Multicomponent Condensation of Aldehydes with Cyclic Ketones

Under microwave irradiation, the one-pot multicomponent condensation reaction of three moles of aromatic aldehydes with two moles of cyclic ketones having free α,α'-methylene positions such as cyclopentanone or cyclohexanone in the presence of ammonium acetate and acetic acid afforded dicycloalkenopyridines with two α-arylidene groups in high yields. Under the similar reaction condition, the reaction of aromatic aldehydes with 1-tetralone having only one α-methylene position alternatively resulted in 10-ary...     

Enantioselective Addition of Diethylzinc to Aldehydes Catalyzed by N-Sulfonylated Amino Alcohols

Asymmetric C-C bond forming reactions are of prime importance in modem synthetic organic chemistry. The use of chiral amino alcohol ligands is widespread in this area.[1] Herein, we describe the synthesis of N-sulfonylated amino alcohols 1～4 and enantioselective addition of diethylzinc to aldehydes was carried out employing titanium(Ⅳ) complexes 1～4.     

Knoevenagel Condensation Catalyzed by 1,1,3,3‐Tetramethylguanidium Lactate

Knoevenagel condensation between malononitrile or ethyl cyanoacetate and carbonyl compounds could be effectively promoted by 1,1,3,3‐tetramethylguanidium lactate, a basic ionic liquid, under mild conditions. Good to high isolated yields could be obtained. The ionic liquid can enhance the reaction rates significantly even though it was used in catalytic amount. The ionic liquid could be prepared simply and reused efficiently.     

Aqueous Knoevenagel Condensation Catalyzed by Aminopropyl-functionalized MCM-41

Since much more attention has been paid to the sustainable development, many researchers try to improve conventional chemical process and find new and more, environmentally friendly routes1. Aqueous-phase reactions are of interest as environ- mentally ben…     

Asymmetric Addition of Diethylzinc to Aldehydes Catalyzed by Chiral γ_Amino Alcohols

Although the asymmetric additions of diethylzinc to aldehydes have been extensively studied in the presence of chiral catalyst, most of the chiral ligands tested are b-amino alcohols1. In this report, the synthesis of chiral gamino alcohols 1-4 from the reaction of (+)-camphor and (-)-menthone with 2-lithiomethyl-6-methyl-pyridine or 2-picolly- lithium2, which give a single diasteromer as determined by 1H NMR with high yields (Scheme 1)3, and their application in the enantioselective additio…     

Condensation of 1-Amino-4-azafluorene with α-Diketones and α,β-Unsaturated Ketones

Condensation of 1-amino-4-azafluorene with -diketones and with unsaturated ketones in basic medium gives novel substituted 1,4-diazafluoranthenes and also dihydro-4-azafluoreno[9,9a,1-b,c]cyclohexano[2',3'-e]- and indano[1',2'-e]azepines.     

Probing α-Amino Aldehydes as Weakly Acidic Pronucleophiles: Direct Access to Quaternary α-Amino Aldehydes by an Enantioselective Michael Addition Catalyzed by Brønsted Bases

The high tendency of α-amino aldehydes to undergo 1,2-additions and their relatively low stability under basic conditions have largely prevented their use as pronucleophiles in the realm of asymmetric catalysis, particularly for the production of quaternary α-amino aldehydes. Herein, it is demonstrated that the chemistry of α-amino aldehydes may be expanded beyond these limits by documenting the first direct α-alkylation of α-branched α-amino aldehydes with nitroolefins. The reaction produces densely functionalized products bearing up to two, quaternary and tertiary, vicinal stereocenters with high diastereo- and enantioselectivity. DFT modeling leads to the proposal that intramolecular hydrogen bonding between the NH group and the carbonyl oxygen atom in the starting α-amino aldehyde is key for reaction stereocontrol.     

Regioselective Synthesis of 2-Functionalized Thiophenes by Condensation of α-Mercapto Compounds with β-Aminoenone Derivatives

2-Acylthiophenes and ethyl 2-thiophene-carboxylates are prepared regioselectively by reaction of 3-ctil oroenones and 2-acylenammoni urn chlorides with α-mercapto derivatives in good to moderate yields.     

Aqueous-Phase Synthesis of α-Hydroxyphosphonates Catalyzed by β-Cyclodextrin

α-Hydroxyphosphonates were synthesized from aromatic/heteroaromatic aldehydes with triethyl phosphite in the presence of β-cyclodextrin in an aqueous medium. The β-cyclodextrin can be recovered and reused without loss of catalytic activity.