Diels-alder reactivity of 1-alkoxyphenyl-3-trialkylsiloxy-1,3-dienes

The synthesis of 1-(3,4,5-trimethoxyphenyl)-3-trialkylsiloxy-1,3-butadienes and their Diels-Alder reaction with selected dienophiles at room temperature is described. These aryldienes are useful building blocks for the synthesis of natural and pharmacological active products, as has been shown by the preparation of a tetracyclic ketone needed for the synthesis of new anthracycline analogues.     

Diels-alder reactivity of polycyclic aromatic hydrocarbons-5: Theoretical correlations

Second-order rate constants for the Diels-Alder reaction of 90 aromatic hydrocarbons with maleic anhydride, measured spectrophotometrically at 91.5° in 1,2,4-trichlorobenzene, are correlated with various reactivity indices, namely Herndon's structure count ratios, second-order perturbation energies, Brown's paralocalization energies, Hess-Schaad resonance energy differences and Polansky indices. Apart from the latter theory, all methods yield satisfactory correlations, with the Hess-Schaad theory being marginally better. An explanation is given why the Hess-Schaad theory is superior to para-localization theory although both are based on Hückel π-electron energies. The observed regioselectivity is correctly accounted for by all except Polansky's theory which yields incorrect results for certain phenes and starphenes.     

Diels-alder reaction of cyclopropenylketone

The Diels-Alder reactions of tris(trifluoromethyl)trifluoroacetyl-cyclopropene with dienes gave syn-adducts mainly, due to the electronic effects of the fluorinated substituents.     

Diels-alder reactions of alumina-and magnesacyclopentadienes

[4π + 2π]-Cycloaddition of substituted alumina-and magnesacyclopenta-2,4-dienes with such dienophiles as maleic anhydride, N-methylmaleimide, 1,4-benzoquinone, and 1,4-naphthoquinone resulted in the formation of the corresponding fused alumina-and magnesanorbornenes whose hydrolysis gave isobenzofuran, isoindole, naphthalene, and anthracene derivatives in high yields.     

Diels-alder cycloaddition reactions of 1,3-diazabutadienes with ketenes

Diels-Alder cycloaddition reactions of 1-aryl-4-dimethylamino-2-phenyl-1,3-diazabutadienes with monophenyl and diphenylketenes, resulting in high yields of pyrimidin-6-one derivatives are reported.     

Diels-alder cycloaddition of tetrachlorothiophene-S,S-dioxide to azulene

The cycloaddition of tetrachlorothiophene-S,S-dioxide to azulene occurs across the 1- and 2-positions to give 1,2,3,4-tetrachlorobenz[a]azulene.     

Diels-alder reactions with ethyl 1-benzofuran-3-carboxylates

Substituted salicylaldehydes reacted with ethyl diazoacetate to give ethyl 1-benzofuran-3-carboxylates containing various substituents in the aromatic ring. The Diels-Alder reaction of these compounds with Danishefsky’s diene was regioselective, and it provided an effective method for the construction of the heterocyclic skeleton of hexahydrodibenzo[b,d]furan-7-one or tetrahydrodibenzo[b,d]furan-7-one. The adducts were found to undergo rearrangement to substituted 4′-hydroxybiphenyl-2-yl methyl carbonates during column chromatography on silica gel.     

Diels-alder reactions with 2-(Arylsulfinyl)-1,4-benzoquinones: effect of aryl substitution on reactivity, chemoselectivity, and pi-facial diastereoselectivity

Diels-Alder reactions of (SS)-2-(2'-methoxynaphthylsulfinyl)-1, 4-benzoquinone (1b), 2-(p-methoxyphenylsulfinyl)-1,4-benzoquinone (1c), and 2-(p-nitrophenylsulfinyl)-1,4-benzoquinone (1d) with cyclopentadiene are reported. These cycloadditions allowed the highly chemo- and stereoselective formation of both diastereoisomeric endo-adducts resulting from reaction on the unsubstituted double bond C(5)-C(6) of quinones working under thermal and Eu(fod)(3)- or BF(3).OEt(2)-catalyzed conditions. The synthesis of endo-adduct [4aS,5S,8R,8aR,SS]-9d resulting from cycloaddition on the substituted C(2)-C(3) double bond was achieved in a chemo- and diastereoselective way from quinone 1d in the presence of ZnBr(2). The reactivity and selectivity of the process proved to be dependent on the electron density of the arylsulfinyl group.     

Simple prediction of cycloaddition orientation: I—Diels-alder reactions

Application of the “hard and soft” concept to the Woodward-Katz model allows simple and accurate prediction of the structure of the major adduct in Diels-Alder reactions. About 100 examples have been examined. Agreement with experimental results is excellent: therefore, the doubts expressed by Houk et al.³⁶ are groundless.Two special cases deserve mention. First, for compounds with heteroatoms at reactive sites, it is necessary to introduce explicity the overlap integrals in the perturbational treatment. Second, in the reactions between electron-poor dienes and nitrosobenzene derivatives the adjacent lone pairs on N and O play an important role.     

土木香内酯和异土木香内酯与共轭二烯的Diels-Alder反应

本文以土木香根中分离得到的土木香内酯(1)和异土木香内酯(2)为原料, 分别与环戊二烯(3)、螺[2.4]-4,6-庚二烯(4)、呋喃、蒽或丙烯醛进行Diels-Alder反应, 发现和2只与3或4发生反应, 未能得到1和2与呋喃、蒽或丙烯醛的反应产物。X射线单晶衍射法确定1或2与3的反应产物的构型, 应用高分辨核磁共振谱NOE方法确定1或2与4的反应产物的构型。     

混合稀土氯化物催化的Diels-Alder反应

本文提出以混合烯土氯化物作为Diels-Alder反应催化剂, 催化三种有工业应用价值的环加成反应。实验结果表明, 混合稀土氯化物对具有含氧基团底物的Diels-Alder反应催化效果显著, 其中混合重烯土氯化物比混合轻稀土氯化物表现出更高的催化活性。。     

Diels-alder reaction of 2-chloro-2-nitrosopropane with 1,3-cyclohexadiene

3-(2-Chloropropyl)-2-oxa-3-azabicyclo[2.2.2]oct-5-ene and 2-oxa-3-azabicyclo[2.2.2]oct-5-ene hydrochloride have been prepared by cycloaddition of 2-chloro-2-nitrosopropane to 1,3-cyclohexadiene and their structure determined by nmr, using a ¹H nmr shift reagent.     

Diels-alder cycloadditions of diene-substituted N-ethoxycarbonyl-2-methyl-1,2-dihydropyridines with N-phenylmaleimide

The ten possible substitution patterns for N-Ethoxycarbonyl-2-methyl-1,2-dihydropyridines 5 in which one or two olefinic sites are alkyl substituted were synthesized and reacted with N-phenylmaleimide 2 to provide cycloadducts 6. N-Ethoxycarbonyl-5,6-cyclohexyl-2-methyl-1,2-dihydropyridine 51 provided the novel spirocycle 61.     

Diels-alder reactions of 1,3-dienes with 4-nitrobenzenediazonium salt as a dienophile

Further examples of the title reaction, discovered by Carlson, Sheppard, and Webster, reveal scope and regiochemistry of the formation of 1,6-dihydropyridazines; all the evidence points to a concerted primary addition.