Diels-Alder reactions as an efficient route to high purity cyclic polymers

A simple and efficient route for the synthesis of cyclic polymer systems is presented. Linear furan protected α-maleimide-ω-cyclopentadienyl functionalized precursors (poly(methyl methacrylate) and poly(tert-butyl acrylate)) were synthesized via atom transfer radical polymerization (ATRP) and subsequent substitution of the bromine end-group with cyclopentadiene. Upon heating at high dilution, deprotection of the dieneophile occurs followed by an intramolecular Diels–Alder reaction yielding a high purity cyclic product.

cis-trans Enantiomerism in the Diels-Alder cycloadducts of 6-arylfulvenes with maleic anhydride: resolution of the exo adducts via the N-((1S)-1-(naphth-1-yl)ethyl)imide derivatives: assignment of the absolute configurations based on the crystal structure of an imide diastereomer

A new case of the uncommon cis-trans enantiomerism is presented. The titled anhydride adducts were prepared in good yields by the known reaction of three 6-arylfulvenes with maleic anhydride (aryl = phenyl, p-tolyl and p-anisyl). The exo adducts were converted to the corresponding imides by reaction with (1S)-1-(naphth-1-yl)ethylamine in similar to 80% yields, and the resulting diastereomeric imides separated by silica gel column chromatography. They were hydrolysed and recyclised to the chiral anhydrides, in `one-pot' with 10% NaOH-EtOH, followed by treatment with 2 M HCl, in similar to 40% yields. The titled anhydrides were thus obtained in homochiral form, in enantiomeric purities (generally) of similar to 90% as indicated by chiral HPLC. The chiral anhydrides were also converted to the corresponding imides (presumably stereospecifically), by treatment with ammonia solution in excellent yields. The crystal structure of one of the above diastereomeric imides (derived from 6-phenylfulvene) was determined, and based on the known (S)-configuration of the naphthylethylamine moiety, the `configurations' of the original anhydride adducts were assigned. (c) 2005 Elsevier Ltd. All rights reserved.

Analysis of geometric and strain effects in homo-Diels-Alder reactions

Molecular mechanics calculations have been carried out to quantify the key geometric and strain effects which are likely to control the homo-Diels-Alder reactivity of 1,4-dienes. The criteria considered include C1..C5 and C2..C4 distances in the diene, twist angle of the two pi units, and the magnitude of strain increase as a result of cycloaddition. By first considering these factors in a number of non-conjugated dienes with known reactivity, the ranges of values within which the reaction is favoured are proposed. Calculations are also reported on several substrates which have not been investigated so far. Promising systems for experimental study are suggested which, in addition to being intrinsically interesting, would place the present proposals on a firm basis.

Self-Assembled Pd6 Open Cage with Triimidazole Walls and the Use of Its Confined Nanospace for Catalytic Knoevenagel- and Diels-Alder Reactions in Aqueous Medium

The two-component self-assembly of a 90 degrees PdII acceptor and a triimidazole donor led to the formation of a water-soluble semi-cylindrical cage with a hydrophobic cavity, which was separately crystallized with hydrophilic- and hydrophobic guests. The parent cage was found to catalyze the Knoevenagel condensation reaction of a series of aromatic mono-aldehydes with active methylene compounds, such as Meldrum's acid or 1,3-dimethylbarbituric acid. The confined hydrophobic nanospace within this cage was also used in the catalytic DielsAlder reactions of 9-hydroxymethylanthracene with N-phenylmaleimide or N-cyclohexylmaleimide.

Impact of carbon dioxide pressurization on liquid phase organic reactions: A case study on Heck and Diels-Alder reactions

Heck coupling reactions of methyl acrylate with various aryl bromides have been investigated using a Pd/TPP catalyst in toluene under pressurized CO2 conditions up to 13 MPa. Although CO2 is not a reactant, the pressurization of the reaction liquid phase with CO2 has positive and negative impacts on the rate of Heck coupling depending on the structures of the substrates examined. In the case of either 2-bromoacetophenone or 2-bromocinnamate, the conversion has a maximum at a CO2 pressure of about 3 MPa; for the former, it is much larger by a factor of 3 compared with that under ambient pressure. For 2-bromobenzene, in contrast, the conversion is minimized at a similar CO2 pressure, being half compared with that at ambient pressure

Marked enantioselectivity enhancements for Diels-Alder reactions in ionic liquids catalysed by platinum diphosphine complexes

Asymmetric Diels-Alder reactions using platinum complexes of BINAP, or of conformationally flexible NUPHOS-type diphosphines, have been compared in dichloromethane and selected ionic liquids. Significant enhancements in the enantioselectivity (Deltaee approximate to 20%), as well as reaction rate, were achieved in ionic liquids compared with the organic media.

Estudo sobre o uso de compostos de nióbio em reações multicomponentes de aza-Diels-Alder

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Darstellung und Diels-Alder-Reaktionen von Bis- und Tris-o-benzochinonen der 9,10-Dihydro-anthracenreihe

Abstract deutsch Die im Rahmen dieser Arbeit dargestellten Anthracen-amphi-chinone wurden durch Oxidation ihrer 9,10-Dihydro-2,3,6,7-tetrahydroxy-Derivate gewonnen, während zwei literaturbekannte Anthracen-amphi-chinone aus den entsprechenden 2,3,6,7-Tetrahydroxy-anthracenen dargestellt wurden. Bei gleicher Substitution wurden identische Produkte gefunden.Die entstandenen Produkte sollten in Diels-Alder-Reaktionen umgesetzt werden. Von allen Hydroxyverbindungen konnten bei der Oxidation mit 2,3-Dichlor-5,6-dicyano-p-benzochinon in Gegenwart von Cyclooctin die entsprechenden Cyclooctin-Addukte erhalten werden. Dadurch wurde nachgewiesen, daß die Oxidationen über die Bis-o-chinone verlaufen, obwohl es nicht gelang, Bis-ortho-benzochinone zu isolieren, die in 9- und 10-Stellung ein Protonen tragen. Stattdessen erhielt man durch eine Keto-Enol-Tautomerie die entsprechenden amphi-Chinone.Drei Bis-chinone wurden direkt mit Cyclooctin umgesetzt und lieferten bei gleicher Substitution die identischen Reaktionsprodukte. Die Cyclooctin-Addukte reagierten beim Bestrahlen durch CO-Eliminierung zu Kohlenwasserstoffen.Bei der Oxidation der Hydroxyverbindungen mit DDQ in Gegenwart von Pentamethyl-cyclopentadien erhielt man die entsprechenden PMCP-Addukte. Dabei reagieren die Chinone als Heterodien.Die Reaktivität von 1,5-Cyclooctadiin mit ortho-Benzochinonen wurde durch die Umsetzung mit 4,5-Dimethyl-ortho-benzochinon untersucht. Dabei wurde festgestellt, daß das Diin mit zwei Molekülen des Chinons reagiert.Mit den erhaltenen Ergebnissen wurde eine Diels-Alder-Polyaddition von 9,10-Dihydro-9,10-ethano-9,10-dimathyl-anthradichinon-(2,3;6,7) mit 1,5-Cyclooctadiin durchgeführt. Bei dieser Reaktion gelangte man zu Oligomeren.

Synthetic application of the diels-alder adduct of β-trans-ocimene and maleic anhydride-II. An approach towards the synthesis of valerenic acid

By a series of reactions the Diels-Alder adduct IV of maleic anhydride and β-trans-Ocimene gave 1-hydroxy-1,4-dimethyl-7-hydroxymethyloctahydroindane (XII). Its further synthetic elaboration furnished 1,4-dimethyl-7-(2-ethoxycarbonyl-1-propenyl)-Δ1-octahydroindane of the valerenic acid skeleton.

Bile-Acids in Asymmetric-Synthesis.2. Cholic-Acid Derived Novel Chiral Auxiliaries For Asymmetric Diels-Alder Reactions

Cholic acid-based chiral acrylate 5 yields a Diels-Alder adduct with cyclopent

An electron rich porous extended framework as a heterogeneous catalyst for Diels-Alder reactions

An electron rich porous metal-organic framework (MOF) has been synthesized, which acts as an effective heterogeneous catalyst for Diels-Alder reactions through encapsulation of the reactants in confined nano-channels of the framework.

无水稀土氯化物催化下Diels-Alder反应的研究

本文研究了在无水氯化稀土催化下2－甲基呋喃和丙烯醛、呋喃和丙烯醛、呋喃和丙烯酸甲酯、2－甲基呋喃和丙烯酸甲酯，呋喃和丙烯酸乙酯以及丁二烯和顺丁烯二酸酐的Diels-Aldel反应，结果表明:（1）无水LnCl_3 (Cn=Nd, Eu, Gd, Yb)对2－甲苯呋喃和丙烯醛的反应有明显的催化作用，反应在温和条件下（25℃，常压无溶剂）顺利进行，不同LnCl_3催化活性按稀土元素原子序数递增而增加。其中，仅用0.008mol% YbCl_3就可催化反应达到85％的产品收率。本反应是连串反应，产物在LnCl_3催化下聚合成低聚物，适当降低催化剂用量是控制产物的聚合从而提高产品收率。与AlCl_3相比，YbCl_3的活性比AlCl_3高。降低反应温度也可以相对控制副反应。当丙烯醛和2－甲基呋喃的用量摩尔比为2:1时，反应能得到最好结果。用THF作溶剂时反应产率比甲苯作溶时要低得多。（2）丙烯醛和呋喃在常温下经CnCl_3催化可得到反应物摩尔比为1：1和2：1两种加成物，主要是2：1加成物。1：1加成物在LnCl_3存在下易聚合，在加热下易聚合。室温下易分角为原料。本反应在－40℃以CH_2Cl_2为溶剂YbCl_3催人时，只得到1：1加成物但收率不高.（3）LnCL_3对呋喃和丙烯酸甲酯的反应有良好的催化活性，当温度为40℃，YbCl_3 10mol%, 反应60小时可得到N/X = 17/27的产物2-carbomethoxy-7-oxabicyclo [2. 2. 1]nept-5-ene, 收率为80％。温度的降低有利地内型产物的生成，反应时间，催化剂用量对反应产物收率和立体选择性都有影响。（4）2－甲基呋喃和丙烯酸甲酯在YbCl_3催化下比（3）的反应更易进行。0℃时，6mol% YbCl_3反应67小时，收率可达88％，产物N/x达3.0。温度的降低有利于内型产物的生成，而反应时间和催化剂用量不影响产物立体选择性。（5）呋喃和丙烯酸乙酯 在10mol% YbCl_3催化下室温反应48小时，得到N／X＝Y_(1.47)的产物44％。温度的降低有利于内型产物的生成，反应时间相对处长有利于产品收率但不影响产品的立体选择性。此外，我们分离得到丙烯酸乙酯和YbCl_3的络合物，证明反应首先是通过YbCl_3和羟基氧的络合，然后再和双烯加成。（6）不同LnCl_3对丁二烯和顺丁烯二酸酐的反应具有不同催化活性，其活性按稀土元素原子序数递增而增加，即：LaCb < PrCl_3 , SmCl_3 < EuCl_3 < GdCl_3 < YbCl_3.

DIELS-ALDER REACTIONS CATALYZED BY LANTHANIDE CHLORIDES

Lanthanide chlorides have been found to catalyze the Diels-Alder synthesis of 2-butoxy-3, 4-dihydro-2H-pyran and several norbornene derivatives under mild conditions. In particular, the heavier lanthanide chlorides are very active catalysts for some (4 + 2) cycloaddition reactions. The catalyst activities and selectivities generally increase with increasing atomic number of the rare earth elements.

无水稀土氯化物催化丁二烯和顺丁烯二酸酐的Diels-Alder反应

稀土化合物在有机合成中特别是在Diels-Alder反应中的应用是近年来稀土化学中最引人注目的研究课题之一。对于某些难进行的Diels-Alder反应,使用Lewis酸作催化剂可缓和反应条件,提高产物收率,改善产物选择性。其中,含稀土离子的Lewis酸在某些反应中显示了比其它Lewis酸更高的催化活性和产物具有更高的选择性。本文报道以丁二烯和顺丁烯二酸酐为原料,用7种简便易得的稀土氯化物催化这一Dies-Alder反应的结果。