Pdf znonanoparticles, as a recyclable heterogeneous catalyst, efficiently promoted the onepot threecomponent mannich reaction of. The mannich reaction is an organic reaction which consists of an amino alkylation of an acidic proton placed next to a carbonyl functional group by formaldehyde and a primary or secondary amine or ammonia. This gives access to the desired central and axial chirality bearing carbinol allenoate by trapping the corresponding allenoatecopper intermediate with isatin. In summary, we have reported amino acidcatalyzed, onepot threecomponent mannich reactions between dihydroxyacetone, panisidine, and aldehydes. A stereoselective threecomponent vinylogous mannichtype reaction vmr of 1,3bistrimethylsily enol ether 7 was therefore investigated and was found to give cyclized chiral dihydropyridinone compound 9 as an adduct. Threecomponent mannichlike reaction of 2aminoimidazole article pdf available in australian journal of chemistry 6412. To access a cheminform abstract, please click on html or pdf. Pdf diastereoselective threecomponent mannich reaction. The conversion is highly diastereoselective, favoring the formation of antiisomers. Mannichtype threecomponent reactions have been performed successfully using microwave heating in conjunction with the use of ionic liquids as heating agents. Bismuth triflatecatalyzed threecomponent mannichtype. Highly e cient onepot three component mannich reaction under solventfree conditions n.
The biomimetic onepot reaction can also be used for the synthesis of amino sugars. A stereoselective three component vinylogous mannich type reaction vmr of 1, 3 bistrimethylsily enol ether 7 was therefore investigated and was found to give cyclized chiral dihydropyridinone compound 9 as an adduct. Onepot three component mannich type reaction catalyzed by functionalized ionic liquid amene yaghoubia, mohammad reza naimijamal a, ali sharifib a research laboratory of green organic synthesis, department of chemistry iran university of science and technology, tehran 16846, iran. Here, the authors report an enantioselective three. Threecomponent agcatalyzed enantioselective vinylogous.
A highly stereoselective threecomponent direct mannich reaction between aromatic aldehydes, ptoluenesulfonamide, and unfunctionalized ketones was achieved through an enolate mechanism for the first time with a bifunctional quinidine thiourea catalyst. Hfotf4 was identified as a highly potent catalyst 0. Microwaveassisted mannichtype threecomponent reactions. Iodine catalyzes mannichtype reaction of aldehydes, benzyl carbamate and silyl ketene acetal in a three component condensation to afford the corresponding cbz protected. In chemistry, a multicomponent reaction or mcr, sometimes referred to as a multicomponent assembly process or mcap, is a chemical reaction where three or more compounds react to form a single product. A highly antidiastereoselective three component mannich reaction of aromatic amines and aromatic aldehydes with cyclohexanone in the presence of silicasupported ferric hydrogensulfate has been. Directtype catalytic three component mannich reaction in aqueous media. In continuation with our endeavours in development of practically useful synthetic methods we herein report a three component mannich type reaction with aldehydes, enolisable ketones and anilines at rt using bromodimethyl. Amberlyst a21 supported cui was found to be a highly efficient novel heterogeneous catalyst for the threecomponent nitromannich reaction between aldehydes, amines and nitroalkanes.
The present paper reports the primary results of three component mannich reaction and 1,5benzodiazepine synthesis catalyzed by silver complex of a tetranitrile ligand. Previously reported agcatalyzed enantioselective vinylogous mannich and azadielsalder reactions of arylsubstituted aldimines herein, we describe the development of a protocol for efficient threecomponent agcatalyzed enantioselective vm reactions of the more demanding alkylsubstituted aldimines, a class of substrates that cannot be. Pdf directtype catalytic threecomponent mannich reaction. Highly e cient onepot threecomponent mannich reaction under. Three component reaction has also been attempted with onepot procedure employing various catalysts4. Mannich type three component reactions have been performed successfully using microwave heating in conjunction with the use of ionic liquids as heating agents. This paper describes a onepot threecomponent mannich reaction, catalyzed by phosphotungstic acid h 3 pw 12 o 40, a heteropoly acid in ionic liquid. The reaction uses imines formed in situ from aldehydes and electronrich anilines to modify phenolic side chains through a mannichtype electrophilic aromatic substitution pathway. The corresponding asymmetric mannich reaction adducts were obtained in moderate to high yields and stereo selectivity in all the cases tested.
Directtype catalytic threecomponent mannich reaction in aqueous media. A threecomponent mannichtype reaction for selective. A mild and practicallyconvenient onepot procedure for the direct mannich reaction has been developed using a condensation of amines, aldehydes and unmodi ed ketones under solvent free. Canadian journal of chemistry canadian science publishing. Homogeneous catalysis, tetranitrile, silver complex, mannich reaction, 2aminoketones, 1,5 benzodiazepine. Squaric acid catalyzed threecomponent mannich reaction of aromatic aldehydes. Catalytic enantioselective threecomponent mannichtype reaction kazem d.
Scope, optimization, and application to the highly enantioselective synthesis of 1,2amino alcohols. Squaric acid catalyzed threecomponent mannich reaction of aromatic aldehydes, aromatic amines and cyclic ketones in water and solventfree conditions at room temperature. The mannich reaction, on the other hand, is synthetically useful for the construction of nitrogencontaining molecules. A new selective bioconjugation reaction is described for the modification of tyrosine residues on protein substrates. The reaction proceeds rapidly and affords the corresponding protected. Pdf a facile solventfree onepot threecomponent mannich. Like d1piperideine in biosynthesis, the chiral 2, 3 dihydropyridinone compound 9 from vmr is a versatile. Direct three component mannich reactions diaryliodonium salts. A facile solventfree onepot threecomponent mannich. Application of high pressure induced by waterfreezing to the. Lianhai zhang, zhiwei li, ruixiang chang, yu chen, wenqin zhang.
Component mannich reaction catalyzed by mesostructured. Mannichtype reaction,9a mannich reaction of acetaldehyde,9b preparation of azole mannich adducts,9c three component domino reactions,9d enantioselective addition of ketones to chalkogenazines,9e synthesis of 1,4thiazines,9f asymmetric mannich reaction of cyclic ketones,9g etc. The mannich reaction is a very powerful tool for constructing carboncarbon bond in organic chemistry. The direct catalytic asymmetric threecomponent mannich reaction. Forthispurpose,acetophenone,benzaldehydeandanilinewere selected as models and the results are summarized in table 1. In chemistry, a multi component reaction or mcr, sometimes referred to as a multi component assembly process or mcap, is a chemical reaction where three or more compounds react to form a single product. Ethane1,2diaminium hydrogen sulfate was synthesised and characterised by nmr and elemental analysis techniques, and found to exhibit high catalytic efficiency towards onepot mannichtype reactions of ketones with aromatic aldehydes and aromatic amines in ethanol. Mannich reaction has been recognized as one of the most classic multicomponent reactions.
The threecomponent mannich reactions proceeded smoothly in reaction time mentioned in table 3 in the presence of 10 mol% of bn under high speed stirring to. A mild, effective and green method for the mannich reaction of aromatic aldehydes, aromatic amines and ketones has been accomplished in good to excellent yields using hydrophobic sba15phprso 3 h in water at room temperature. Multicomponent reactions mcrs are convergent reactions, in which three or more starting materials react to form a product, where basically all or most of the atoms contribute to the newly formed product. Journal of the american chemical society 2002, 124 5, 827833. View the article pdf and any associated supplements and figures for a period of 48 hours. Polyelectrolyte bronsted acid catalyzed threecomponent mannich reactions with some more ketones various ketones were further investigated to demonstrate the pronounced. Various phosphoric acids, prepared from binol and h8binol derivatives, have been evaluated for catalyzing the direct mannich reaction. In an mcr, a product is assembled according to a cascade of elementary chemical reactions. Excellent enantioselectivities were achieved for a variety of substrates at a typical catalyst loading of merely 0. In the presence of zrcl4, the three component mannich type reaction via a variety of in situ generated aldimines with various ketones, methylenebismethoxybenzaldehyde and aromatic amines in.
The reason for the higher reactivity of aldimine versus aldehyde in proline. The conversion is highly diastereoselective, favoring. Squaric acid catalyzed three component mannich reaction of aromatic aldehydes, aromatic amines and. An efficient, mild, solventfree, onepot threecomponent mannich reaction catalyzed by c 4 h 12 n 2 2 bicl 6clh 2 o h. Supporting information reactions accelerated by emulsion. Pdf threecomponent mannichlike reaction of 2aminoimidazole. Onepot threecomponent mannich reactions of ketones with aromatic aldehydes and aromatic amines are effectively catalyzed by molecular. Threecomponent mannichtype reaction catalyzed by iodine. A threecomponent mannichtype reaction of aromatic aldehydes, anilines, and cyclohexanone in the presence of amberlyst15 affords the corresponding. Safa, mahtab abolfathi, and khatereh ghorbanpour journal of chemical research 2012 36. Heteropoly acids efficiently catalyzed the onepot, threecomponent mannich reaction of ketones with aromatic aldehydes and different amines. The advantages of this new method are a short reaction time 2 h, high yields, easy workup, convenience, low cost, and ecofriendly protocol. The prolinecatalyzed direct asymmetric three component mannich reaction. Mannich type reaction,9a mannich reaction of acetaldehyde,9b preparation of azole mannich adducts,9c three component domino reactions,9d enantioselective addition of ketones to chalkogenazines,9e synthesis of 1,4thiazines,9f asymmetric mannich reaction of cyclic ketones,9g etc.
Squaric acid catalyzed three component mannich reaction of aromatic aldehydes, aromatic amines and cyclic ketones in water and solventfree conditions at room temperature. Onepot multicomponent nitromannich reaction using a. Onepot threecomponent mannich reaction catalyzed by iodine. An efficient, mild, solventfree, onepot three component mannich reaction catalyzed by c 4 h 12 n 2 2 bicl 6clh 2 o h. The reactions proceeded with high chemo and stereoselectivity and furnished the corresponding. Direct catalytic asymmetric threecomponent mannich.
Bond cleavage, fragment modification and reassembly in. As such, 6 h was considered the ideal reaction time. Feb 01, 20 the mannich reaction is a very powerful tool for constructing carboncarbon bond in organic chemistry. Squaric acid catalyzed highly efficient threecomponent. Mediated mannich and aldol reactions yujiro hayashi. Onepot three component mannich reaction in water catalyzed by ecofriendly, hydrophobic and recyclable sulfonic acid based nanosilica sba15phprso 3 h d. Enantioselective threecomponent aminomethylation of. Pdf a threecomponent reaction of 2aminoimidazole with various aldehydes and amines is described that generates 4substituted. Dec 31, 2008 previously reported agcatalyzed enantioselective vinylogous mannich and azadielsalder reactions of arylsubstituted aldimines herein, we describe the development of a protocol for efficient three component agcatalyzed enantioselective vm reactions of the more demanding alkylsubstituted aldimines, a class of substrates that cannot be. In continuation with our endeavours in development of practically useful synthetic methods we herein report a three component mannichtype reaction with aldehydes, enolisable ketones and anilines at rt using bromodimethyl. An environmentallyfriendly, onepot multicomponent reaction of various aldehydes, amines and nitroalkanes for the synthesis of. Aminoacids as the amine component in the mannich reaction. Application of high pressure induced by waterfreezing to.
The next step of mechanism is the formation of enol 7 from acetophenone 1 in. The involvement of the mannich reaction has been proposed in many biosynthetic pathways, especially for alkaloids. The catalyst was found to be mild and efficient, and the protocol affords. Proline catalyzed twocomponent, threecomponent and self. In the presence of a truly catalytic amount of the phosphoric acid, antiselective mannich reactions of cyclic ketones with a wide scope of aldimines were obtained in high. To the best of our knowledge this is the first report of one pot three component mannich reaction catalyzed by a tetranitrile silver complex. The reaction uses imines formed in situ from aldehydes and electronrich anilines to modify phenolic side chains through a mannich type electrophilic aromatic substitution pathway. Pdf highly efficient onepot threecomponent mannich reaction. The proline catalyzed twocomponent and threecomponent asymmetric mannich reaction with hydroxyacetone and selfmannich reaction with propanal were performed successfully under ultrasonic conditions in 1 h to afford mannich products in 9098% isolated yields and 8199% ees with excellent diastereoselectivities. By definition, multicomponent reactions are those reactions whereby more than two reactants combine in a sequential manner to give highly selective products that retain majority of the.
Highly enantioselective threecomponent direct mannich. Iodine, mannich reaction, aldehydes, benzyl carbamate, silyl ketene acetal. Thedirectandenantioselective,onepot,three component,cross. The catalytic activity of hnmpclzncl2sba15 was investigated towards the onepot three component mannich type reaction to a series of aldehydes, ketones, and amines and provided excellent. Thedirectandenantioselective,onepot,three component. The challenges for the design of this threecomponent reaction are threefold.
Transition metal saltcatalyzed direct threecomponent mannich reactions of aldehydes, ketones, and carbamates. The prolinecatalyzed direct asymmetric threecomponent mannich reaction. Highly e cient onepot threecomponent mannich reaction under solventfree conditions n. Onepot threecomponent mannichtype reaction catalyzed by functionalized ionic liquid amene yaghoubia, mohammad reza naimijamal a, ali sharifib a research laboratory of green organic synthesis, department of chemistry iran university of science and technology, tehran 16846, iran. Highly efficient onepot threecomponent mannich reaction in.
Introduction carl mannich first recognized the enormous significance of aminoalkylation of chacidic compounds, and then he extended the chemistry into a broad based synthetic procedure through systematic research arend et al. This protocol has several advantages such as good yields, mild conditions, novel organocatalyst, and good anti selectivities. Directtype catalytic threecomponent mannich reaction in. Direct catalytic asymmetric threecomponent mannich reactions. Highly enantioselective, amino acidcatalyzed, onepot three component asymmetric mannich reactions between dihydroxyacetone, panisidine, and aldehydes are presented. The direct catalytic asymmetric threecomponent mannich. Threecomponent reaction has also been attempted with onepot procedure employing various catalysts4. The corresponding asymmetric mannich reaction adducts were obtained in moderate to high yields and stereo selectivity. Component asymmetric mannich reaction catalyzed by a. A stereoselective three component vinylogous mannich type reaction vmr of 1,3bistrimethylsily enol ether 7 was therefore investigated and was found to give cyclized chiral dihydropyridinone compound 9 as an adduct.
Cheminform is a weekly abstracting service, delivering concise information at a glance that was extracted from about 200 leading journals. The former three research groups used chiral organometallic catalysts, while the latter two employed proline as an organocatalyst. No reaction was observed in the absence of bn table 1, entry 1. A highly antidiastereoselective threecomponent mannich reaction of aromatic amines and aromatic aldehydes with cyclohexanone in the presence of silicasupported ferric hydrogensulfate has been. This new method consistently has the advantages of excellent yields, short reaction times, and nontoxic nature and reusability of the catalyst. Onepot threecomponent mannichtype reaction catalyzed by. Screen catalyst loading for mannich reaction of three components a entry catalyst loading mol% timeh yield% b 1 0. Box 14335186, tehran, iran borganic chemistry research lab. Onepot threecomponent mannich reaction in water catalyzed. Bismuth triflate catalyzes the mannich type reaction of a variety of in situ generated aldimines using aldehydes, anilines, and silyl enol ethers in a three component reaction. This manuscript describes the first example of silver ion complex of a dendritic tetranitrile ligand catalyzed onepot three component mannich reaction and 1,5benzodiazepine synthesis. Mar 16, 2017 a highly efficient direct asymmetric three. An efficient, mild, solventfree, onepot threecomponent mannich reaction catalyzed by c 4 h 12 n 2 2 bicl 6 clh 2 o. Onepot three component mannich reaction catalyzed by sucrose char sulfonic acid.
Multicomponent reactions allow complex structures to be rapidly built from simple starting materials. By definition, multicomponent reactions are those reactions whereby more than two reactants combine in a sequential manner to give. Diastereoselective threecomponent mannich reaction catalyzed by silicasupported ferric hydrogensulfate. Direct three component mannich reactions diaryliodonium. Transition metal saltcatalyzed direct three component mannich reactions of aldehydes, ketones, and carbamates. Frontiers of chemical engineering in china 2009, 3 2, 201205. The reaction takes place under mild ph and temperature conditions and can modify protein.
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