Domino Diels-Alder Research Articles

Pericyclic Cascade Reactions Affording Thienyl- and Benzo[b]thienyl-Fused Architectures: A Synthetic and Density Functional Theory Analysis of Asynchronous Diels-Alder Reactions of Thioarylmaleimides.

Herein, we report the synthesis and characterization of a series of thioarylmaleimides and their varied propensity toward highly selective domino Diels-Alder (D-A)/rearrangement, D-A/ene/elimination, and D-A/oxidation reactions to give three types of thienyl-fused architectures. Stereochemical assignment was achieved using a combination of nuclear magnetic resonance (NMR) studies, gauge independent atomic orbital (GIAO) NMR chemical shift calculations, and DP4+ analysis. Transition-state calculations support an asynchronous concerted mechanism and provide support for rationalizing the observed regio- and stereoselectivity.

Beyond Diels-Alder: Domino reactions in furan-maleimide click networks

The furan-maleimide Diels-Alder chemistry has emerged as an important tool to design thermo-reversible click networks. This not only preserves the strong and robust properties of thermo-sets and rubbers, but also makes it possible to cleave crosslinks at non-degradative temperatures, or in other words to recycle them. In this work a new reaction is reported in furan-maleimide click networks, which is the Double-Diels-Alder reaction (DDA), also known as domino Diels-Alder. This forms extra linkages between Diels-Alder adducts and non-reacted furan groups and evidently leads to stronger materials, but also prevents efficient thermal (re)cycling. This work shows with nuclear magnetic resonance (NMR) characterization, differential scanning calorimetry (DSC) and rheology that the DDA reaction can occur both in intramolecular and intermolecular fashion, but also that it exhibits reversibility just like the regular Diels-Alder reaction. This reaction can be easily overlooked creating what at first sight might be inexplicable reactivity when analyzing the properties of furan-maleimide click networks.

Efficient synthesis of polyfunctionalized carbazoles and pyrrolo[3,4-c]carbazoles via domino Diels-Alder reaction.

The p-TsOH-catalyzed Diels–Alder reaction of 3-(indol-3-yl)maleimides with chalcone in toluene at 60 °C afforded two diastereoisomers of tetrahydropyrrolo[3,4-c]carbazoles, which can be dehydrogenated by DDQ oxidation in acetonitrile at room temperature to give the aromatized pyrrolo[3,4-c]carbazoles in high yields. On the other hand, the one-pot reaction of 3-(indol-3-yl)-1,3-diphenylpropan-1-ones with chalcones or benzylideneacetone in acetonitrile in the presence of p-TsOH and DDQ resulted in polyfunctionalized carbazoles in satisfactory yields. The reaction mechanism included the DDQ oxidative dehydrogenation of 3-(indol-3-yl)-1,3-diphenylpropan-1-ones to the corresponding 3-vinylindoles, their acid-catalyzed Diels–Alder reaction and sequential aromatization process.

Leo A. Paquette

Leo A. Paquette, 85, died on Jan. 21 in Columbus, Ohio. “Leo was a prolific organic chemist. His research contributions included heterocyclic chemistry, natural products synthesis, and properties of architecturally interesting compounds. I am particularly fond of his combination of domino Diels-Alder reactions and photochemistry to prepare the unsaturated hydrocarbon triquinacene. Leo is best known for the first synthesis of dodecahedrane, which also started with a domino Diels-Alder reaction. Leo was tireless in his service to the chemistry community—for example, on the editorial boards of Organic Syntheses and Organic Reactions.”—David J. Hart, friend and colleague Most recent title: Distinguished University Professor, Ohio State University Education: BS, chemistry, Holy Cross College, 1956; PhD, chemistry, Massachusetts Institute of Technology, 1959 Survivors: Wife, Estelle; son, Ron; daughters, Donna, Linda, Lisa, and Susan To recognize your late loved one or colleague, submit obituary information at ...

Short Access to Belt Compounds with Spatially Close C=C Bonds and Their Transannular Reactions.

Two domino Diels-Alder adducts were obtained from 3,7-bis(cyclopenta-2,4-dien-1-ylidene)-cis-bicyclo[3.3.0]octane and dimethyl acetylenedicarboxylate or N-methylmaleimide under microwave irradiation. From the first adduct, a C20H24 diene with C2v symmetry was obtained by Zn/AcOH reduction, hydrolysis, oxidative decarboxylation, and selective hydrogenation. Photochemical [2+2] cycloaddition of this diene gave a thermally unstable cyclobutane derivative, which reverts to the diene. However, both the diene and the cyclobutane derivatives could be identified by X-ray diffraction analysis upon irradiation of the diene crystal. New six-membered rings are formed upon the transannular addition of bromine or iodine to the diene. The N-type selectivity of the addition was examined by theoretical calculations, which revealed the distinct susceptibility of the doubly bonded carbon atoms to the bromine attack.

From central to helical chirality: synthesis of P and M enantiomers of [5]helicenequinones and bisquinones from (SS)-2-(p-tolylsulfinyl)- 1,4-benzoquinone.

The reaction of 1,4-divinyl-1,3-cyclohexadiene, 5,8-dimethoxy- or tert-butyldimethylsilyloxy-3-vinyl-1,2-dihydrophenanthrene or 6-vinyl-7,8-dihydro-1,4-phenanthrenequinone with an excess of enantiopure (SS)-2-(p-tolylsulfinyl)-1,4-benzoquinone (2) led to the direct formation of enantioenriched dihydro[5]helicenequinones or bisquinones (50-->98 % ee). A domino Diels-Alder cycloaddition/sulfoxide elimination/partial aromatization process occurs, being the absolute configuration of the final helicene defined in the aromatization step. Both M and P helimers are accessible through a stepwise enantiodivergent process if the pentacyclic dihydroaromatic intermediate resulting in the two first steps is aromatized in the presence of (+/-)-2, DDQ, CAN or DBU.

Preparation of 9,9-dimethoxytetracyclo[8.5.0.0 2,8.0 7,11]pentadeca-3,5,12,14,-tetraene and conversion to hexacyclo[8.5.1.1 4,7.0 5,14.0 6,12.0 11,15.0 16,17]heptadeca-2,8-diene-13-one using a domino Diels-Alder reaction

The easily prepared bishomosecoheptaprismane ring system of 1 was converted to the tetracyclo[8.5.0.0 2,8.0 7,11]pentadeca-3,5,12,14-tetraene ring system of 10 using a photochemical decarbonylation/fragmentation reaction as the key step. The closely held face-to-face butadiene units in 10 undergo [4+4]cycloaddition under photochemical conditions and participate in domino Diels-Alder reactions with maleic anhydride and dicyanoacetylene. The maleic anhydride domino Diels-Alder adduct 18 was converted to the previously unreported hexacyclo[8.5.1.1 4,7.0 5,14.0 6,16.0 11,15.0 16,17]heptadecane ring system embodied in 19. A single crystal X-ray analysis of 20, one member of this new ring system, is reported and the results are compared with ab initio molecular orbital calculations.

A novel photochemical rearrangement of 1,3-diaryl-1,2-dihydropentalenes to the 1,5-isomers and their domino Diels-Alder reactions

Abstract Novel photochemical rearrangement of 1,3-diaryl-1,2-dihydropentalenes to 1,5-isomers and the subsequent domino Diels-Alder reactions of the latter with maleic anhydride are described. Synthesis, photorearrangement and subsequent domino Diels-Alder reactions of 1,3-diaryl-1,2-dihydropentalenes are described.

Synthesis of a versatile functionalized tetraquinane. Convenient access to 1,3-bishomopentaprismanedione

The tetracyclic diene dione 1 has been synthesized by a short oxidative decarboxylation route starting with the domino Diels-Alder adduct 2. Photocyclization of the bisketal of 1 was used to arrive expediently at 1,3-bishomopentaprismanedione (7).

Domino Diels-Alder reactions. 6. Domino Diels-Alder cycloadditions to 9,10-dihydrofulvalene and 11,12-dihydrosesquifulvalene. A synthetic tool for the elaboration of polycondensed alicyclic systems

Domino Diels-Alder reactions. 6. Domino Diels-Alder cycloadditions to 9,10-dihydrofulvalene and 11,12-dihydrosesquifulvalene. A synthetic tool for the elaboration of polycondensed alicyclic systems

ChemInform Abstract: DOMINO DIELS‐ALDER REACTIONS. 4. C16‐HEXAQUINACENE

Chemischer InformationsdienstVolume 9, Issue 25 Isocyclic Compounds ChemInform Abstract: DOMINO DIELS-ALDER REACTIONS. 4. C16-HEXAQUINACENE L. A. PAQUETTE, L. A. PAQUETTESearch for more papers by this authorR. A. SNOW, R. A. SNOWSearch for more papers by this authorJ. L. MUTHARD, J. L. MUTHARDSearch for more papers by this authorT. CYNKOWSKI, T. CYNKOWSKISearch for more papers by this author L. A. PAQUETTE, L. A. PAQUETTESearch for more papers by this authorR. A. SNOW, R. A. SNOWSearch for more papers by this authorJ. L. MUTHARD, J. L. MUTHARDSearch for more papers by this authorT. CYNKOWSKI, T. CYNKOWSKISearch for more papers by this author First published: June 20, 1978 https://doi.org/10.1002/chin.197825142Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume9, Issue25June 20, 1978 RelatedInformation

Domino Diels-Alder reactions. I. Applications to the rapid construction of polyfused cyclopentanoid systems

Domino Diels-Alder reactions. I. Applications to the rapid construction of polyfused cyclopentanoid systems