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. Journal of the american chemical society 2002, 124 5, 827833. The biomimetic onepot reaction can also be used for the synthesis of amino sugars. Squaric acid catalyzed three component mannich reaction of aromatic aldehydes, aromatic amines and. This protocol has several advantages such as good yields, mild conditions, novel organocatalyst, and good anti selectivities. 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. Mannichtype threecomponent reactions have been performed successfully using microwave heating in conjunction with the use of ionic liquids as heating agents. Mar 16, 2017 a highly efficient direct asymmetric three. Safa, mahtab abolfathi, and khatereh ghorbanpour journal of chemical research 2012 36. The mannich reaction is a very powerful tool for constructing carboncarbon bond in organic chemistry. Directtype catalytic three component mannich reaction in aqueous media.
Direct catalytic asymmetric threecomponent mannich reactions. Onepot threecomponent mannich reaction catalyzed by iodine. The present paper reports the primary results of three component mannich reaction and 1,5benzodiazepine synthesis catalyzed by silver complex of a tetranitrile ligand. In summary, we have reported amino acidcatalyzed, onepot threecomponent mannich reactions between dihydroxyacetone, panisidine, and aldehydes. The prolinecatalyzed direct asymmetric threecomponent mannich reaction. 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. Lianhai zhang, zhiwei li, ruixiang chang, yu chen, wenqin zhang. Thedirectandenantioselective,onepot,three component.
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. An efficient, mild, solventfree, onepot threecomponent mannich reaction catalyzed by c 4 h 12 n 2 2 bicl 6clh 2 o h. Scope, optimization, and application to the highly enantioselective synthesis of 1,2amino alcohols. Feb 01, 20 the mannich reaction is a very powerful tool for constructing carboncarbon bond in organic chemistry. Iodine, mannich reaction, aldehydes, benzyl carbamate, silyl ketene acetal. Application of high pressure induced by waterfreezing to the. Heteropoly acids efficiently catalyzed the onepot, threecomponent mannich reaction of ketones with aromatic aldehydes and different amines. 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. 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. 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.
Excellent enantioselectivities were achieved for a variety of substrates at a typical catalyst loading of merely 0. In an mcr, a product is assembled according to a cascade of elementary chemical reactions. Microwaveassisted mannichtype threecomponent reactions. The involvement of the mannich reaction has been proposed in many biosynthetic pathways, especially for alkaloids.
Pdf threecomponent mannichlike reaction of 2aminoimidazole. To access a cheminform abstract, please click on html or pdf. This gives access to the desired central and axial chirality bearing carbinol allenoate by trapping the corresponding allenoatecopper intermediate with isatin. Onepot multicomponent nitromannich reaction using a. Mannich reaction has been recognized as one of the most classic multicomponent reactions. The prolinecatalyzed direct asymmetric three component mannich reaction. Box 14335186, tehran, iran borganic chemistry research lab. Highly enantioselective threecomponent direct mannich. An efficient, mild, solventfree, onepot threecomponent mannich reaction catalyzed by c 4 h 12 n 2 2 bicl 6 clh 2 o.
A threecomponent mannichtype reaction of aromatic aldehydes, anilines, and cyclohexanone in the presence of amberlyst15 affords the corresponding. Threecomponent mannichtype reaction catalyzed by iodine. Highly e cient onepot three component mannich reaction under solventfree conditions n. The conversion is highly diastereoselective, favoring. Cheminform is a weekly abstracting service, delivering concise information at a glance that was extracted from about 200 leading journals. 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. Screen catalyst loading for mannich reaction of three components a entry catalyst loading mol% timeh yield% b 1 0. Diastereoselective threecomponent mannich reaction catalyzed by silicasupported ferric hydrogensulfate. Three component mannich reaction and 1,5benzodiazepine. 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 threecomponent mannich reaction of aromatic aldehydes, aromatic amines and cyclic ketones in water and solventfree conditions at room temperature.
A facile solventfree onepot threecomponent mannich. Direct three component mannich reactions diaryliodonium salts. 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. The former three research groups used chiral organometallic catalysts, while the latter two employed proline as an organocatalyst. The reaction uses imines formed in situ from aldehydes and electronrich anilines to modify phenolic side chains through a mannichtype electrophilic aromatic substitution pathway. An environmentallyfriendly, onepot multicomponent reaction of various aldehydes, amines and nitroalkanes for the synthesis of. Good product yields and short reaction times have been achieved.
Pdf a facile solventfree onepot threecomponent mannich. Pdf diastereoselective threecomponent mannich reaction. The advantages of this new method are a short reaction time 2 h, high yields, easy workup, convenience, low cost, and ecofriendly protocol. By definition, multicomponent reactions are those reactions whereby more than two reactants combine in a sequential manner to give. 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. Application of high pressure induced by waterfreezing to. The corresponding asymmetric mannich reaction adducts were obtained in moderate to high yields and stereo selectivity. A highly antidiastereoselective threecomponent mannich reaction of aromatic amines and aromatic aldehydes with cyclohexanone in the presence of silicasupported ferric hydrogensulfate has been. Onepot threecomponent mannichtype reaction catalyzed by. Pdf znonanoparticles, as a recyclable heterogeneous catalyst, efficiently promoted the onepot threecomponent mannich reaction of. A threecomponent mannichtype reaction for selective. The catalyst was found to be mild and efficient, and the protocol affords.
Squaric acid catalyzed threecomponent mannich reaction of aromatic aldehydes. Highly efficient onepot threecomponent mannich reaction in. Pdf directtype catalytic threecomponent mannich reaction. This method provides a novel and improved modification of the threecomponent mannich reaction in terms of mild reaction conditions. 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. Onepot threecomponent mannich reaction in water catalyzed. 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. Supporting information reactions accelerated by emulsion. Component asymmetric mannich reaction catalyzed by a.
The corresponding asymmetric mannich reaction adducts were obtained in moderate to high yields and stereo selectivity in all the cases tested. This paper describes a onepot threecomponent mannich reaction, catalyzed by phosphotungstic acid h 3 pw 12 o 40, a heteropoly acid in ionic liquid. Here, the authors report an enantioselective three. 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.
Mannich type three component reactions have been performed successfully using microwave heating in conjunction with the use of ionic liquids as heating agents. Transition metal saltcatalyzed direct threecomponent mannich reactions of aldehydes, ketones, and carbamates. Highly e cient onepot threecomponent mannich reaction under. The reaction takes place under mild ph and temperature conditions and can modify protein. Mediated mannich and aldol reactions yujiro hayashi. Bismuth triflatecatalyzed threecomponent mannichtype. Multicomponent reactions allow complex structures to be rapidly built from simple starting materials. View the article pdf and any associated supplements and figures for a period of 48 hours. Directtype catalytic threecomponent mannich reaction in. 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. 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.
Direct catalytic asymmetric threecomponent mannich. Highly enantioselective, amino acidcatalyzed, onepot three component asymmetric mannich reactions between dihydroxyacetone, panisidine, and aldehydes are presented. Canadian journal of chemistry canadian science publishing. Continuous flow enantioselective three component antimannich. The next step of mechanism is the formation of enol 7 from acetophenone 1 in. The direct catalytic asymmetric threecomponent mannich. Onepot three component mannich reaction catalyzed by sucrose char sulfonic acid. Squaric acid catalyzed three component mannich reaction of aromatic aldehydes, aromatic amines and cyclic ketones in water and solventfree conditions at room temperature. The challenges for the design of this threecomponent reaction are threefold.
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 reactions proceeded with high chemo and stereoselectivity and furnished the corresponding. A new selective bioconjugation reaction is described for the modification of tyrosine residues on protein substrates. 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. Frontiers of chemical engineering in china 2009, 3 2, 201205. 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. Enantioselective threecomponent aminomethylation of. The reaction proceeds rapidly and affords the corresponding protected. Onepot three component mannich reaction in water catalyzed by ecofriendly, hydrophobic and recyclable sulfonic acid based nanosilica sba15phprso 3 h d. Directtype catalytic threecomponent mannich reaction in aqueous media. 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.
The conversion is highly diastereoselective, favoring the formation of antiisomers. Catalytic enantioselective threecomponent mannichtype reaction kazem d. The direct catalytic asymmetric threecomponent mannich reaction. Transition metal saltcatalyzed direct three component mannich reactions of aldehydes, ketones, and carbamates. Bond cleavage, fragment modification and reassembly in. 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.
Threecomponent mannichlike reaction of 2aminoimidazole article pdf available in australian journal of chemistry 6412. Like d1piperideine in biosynthesis, the chiral 2, 3 dihydropyridinone compound 9 from vmr is a versatile. No reaction was observed in the absence of bn table 1, entry 1. Threecomponent reaction has also been attempted with onepot procedure employing various catalysts4. Forthispurpose,acetophenone,benzaldehydeandanilinewere selected as models and the results are summarized in table 1. 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. This new method consistently has the advantages of excellent yields, short reaction times, and nontoxic nature and reusability of the catalyst. Three component reaction has also been attempted with onepot procedure employing various catalysts4.
To the best of our knowledge this is the first report of one pot three component mannich reaction catalyzed by a tetranitrile silver complex. 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. Aminoacids as the amine component in the mannich reaction. Hfotf4 was identified as a highly potent catalyst 0. Homogeneous catalysis, tetranitrile, silver complex, mannich reaction, 2aminoketones, 1,5 benzodiazepine.
A highly antidiastereoselective three component mannich reaction of aromatic amines and aromatic aldehydes with cyclohexanone in the presence of silicasupported ferric hydrogensulfate has been. Direct three component mannich reactions diaryliodonium. An efficient, mild, solventfree, onepot three component mannich reaction catalyzed by c 4 h 12 n 2 2 bicl 6clh 2 o h. 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. 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. 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. Onepot threecomponent mannich reactions of ketones with aromatic aldehydes and aromatic amines are effectively catalyzed by molecular. The reason for the higher reactivity of aldimine versus aldehyde in proline. Polyelectrolyte bronsted acid catalyzed threecomponent mannich reactions with some more ketones various ketones were further investigated to demonstrate the pronounced. Highly e cient onepot threecomponent mannich reaction under solventfree conditions n. As such, 6 h was considered the ideal reaction time.
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. Threecomponent agcatalyzed enantioselective vinylogous. Squaric acid catalyzed highly efficient threecomponent. Pdf highly efficient onepot threecomponent mannich reaction. Proline catalyzed twocomponent, threecomponent and self. 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. Various phosphoric acids, prepared from binol and h8binol derivatives, have been evaluated for catalyzing the direct mannich reaction. Component mannich reaction catalyzed by mesostructured.
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