Search results for "cycloaddition"
showing 10 items of 392 documents
A Click‐Functionalized Single‐Molecule Magnet Based on Cobalt(II) and Its Analogous Manganese(II) and Zinc(II) Compounds
2014
A mononuclear CoII single-molecule magnet suitable for click chemistry was investigated. [M(oda)(aterpy)] complexes (oda2– = oxodiacetate, aterpy = 4′-azido-2,2′:6′,2″-terpyridine) with M = MnII, ZnII, and CoII were synthesized as azide-functionalized building blocks for the copper-catalyzed azide–alkyne cycloaddition reaction. The required structural integrity of the complexes in solution was proven in great detail by using ESI-MS and NMR spectroscopy. For the six-coordinate [Co(oda)(aterpy)] complex, single-molecule magnet behavior was confirmed with an effective energy barrier of 4.2 cm–1.
Cycloadditionen von 2H ‐Benzo[ b ]thiet und Verbindungen mit kumulierten Doppelbindungen
1994
Cycloaddition Reactions of 2H-Benzo[b]thiete and Compounds with Cumulated Double Bonds o-Thiobenzoquinone methide (2), generated by thermal ring opening of 2H-benzo[b]thiete (1), reacts with allene 3, ketene imine 7, the carbodiimides 9a-c, and the N-sulfinylamines 11a-c in highly specific [8π + 2π] cycloaddition processes to form novel types of heterocyclic systems 4, 8, 10a-c, and 12a-c with exocyclic double bonds. The 1:1 adduct 4 can add a further molecule of allene to yield the spiro compounds 5 and 6.
Die Cycloaddition von 4‐Phenyl‐1,2,4‐triazolin‐3,5‐dion an 9,10‐Diallylidenbicyclo[6.2.0]deca‐1(8),2,6‐trien
1985
Das Dimere 2 von 1,5-Cyclooctadien-3-in (1) bildet mit 4-Phenyl-1,2,4-triazolin-3,5-dion (PTD) ein Bisaddukt 6. Nach den spektroskopischen Daten kommt eine der symmetrischen Strukturen a–d in Frage. Die Rontgenstrukturanalyse beweist die Konstitution c. Die beiden PTD-Molekule reagieren demnach nicht nur in einer doppelten regiospezifischen [π2s + π4s]-Cycloaddition, sondern greifen auch stereospezifisch von derselben Seite an. Von den Rontgenstrukturdaten ist besonders die Konformation des Tricyclo[8.6.0.02,9]hexadeca-3,8,11,16-tetraen-Grundgerustes hervorzuheben, die aus zwei bootformigen Achtringen und einem zentralen, leicht gefalteten Vierring besteht. Cycloaddition of 4-Phenyl-1,2,4-t…
Thermische Cycloadditionen von 1,2‐Dihydropentalen
1989
1,2-Dihydropentalen (1) ist ein gekreuzt konjugiertes 6π-Elektronensystem, das in thermischen Cycloadditionen als 2π-, 4π- oder 6π-Komponente fungieren kann. Es werden die Additionen an Tetraphenylcyclopentadienon (1+23), N-Phenylmaleinimid (1+45) und Tropon (1+68 bzw. 10) beschrieben. Auf der Basis von MNDO-Rechnungen werden Peri-, Regio- und Stereoselektivitat anhand von primaren und sekundaren Orbitalwechselwirkungen diskutiert. Thermal Cycloaddition of 1,2-Dihydropentalene 1,2-Dihydropentalene (1) is a cross-conjugated 6π-electron system, that can act in thermal cycloaddition processes as a 2π, 4π, or 6π component. The addition reactions with tetraphenylcyclopentadienone (1+23), N-pheny…
Herstellung von 1,5‐Cyclooctadiin und 1,3,5,7‐Cyclooctatetraen aus 1,5‐Cyclooctadien
1994
Preparation of 1,5-Cyclooctadiyne and 1,3,5,7-Cyclooctatetraene from 1,5-Cyclooctadiene Bromination of 1,5-cyclooctadiene (1) and stepwise dehydro-bromination first with KOtBu and then with KOtBu/18-crown-6 yields 1,5-cyclooctadiyne (5). A prolonged interaction of the base causes a complete transformation to cyclooc-tatetraene (6). Diyne 5 and even more the intermediate enyne 4 are highly reactive dienophiles. The cycloadducts 10–14 formed with 1,3-cyclohexadiene, carbon disulfide, and tetraphenylcyclopentadienone were isolated and characterized. Treatment of 5 with titanium tetrachloride induces a vigorous polymerization.
Kinetische Untersuchungen zu Diels‐Alder‐Reaktionen des Cyclooctins mit anschließender Aromatisierung
1984
Aus Cyclooctin (1) und den cyclischen Dienen 2a – g entstehen die Tricyclen 3a – g, die ganz unterschiedliche Stabilitat aufweisen. 3a, b, f und g zerfallen spontan. Unter Abspaltung von CO2, SO2, CO und N2 entstehen die aromatischen Verbindungen 4a – c. 3c eliminiert beim Erhitzen C2H4. 3e wird thermisch kaum mehr gespalten, aber ganz effizient bei der Photolyse, und 3d ist schlieslich gegenuber einer Aromatisierung stabil. Die thermische Ethylenabspaltung und die doppelte Photodecarbonylierung werden kinetisch untersucht. Kinetic Investigations of Diels-Alder-Reactions of Cyclooctyne with Consecutive Aromatization The tricyclic compounds 3a – g, generated from cyclooctyne (1) and the cycl…
Cycloadditionen von Benzothiet und aromatischen Nitroso‐Verbindungen
1993
Cycloaddition Reactions of Benzothiete and Aromatic Nitroso Compounds The new heterocyclic ring systems 4H-3,1,2-benzoxathiazines 4 and 2,3-dihydro-1,2-benzothiazol 1-oxides 6 can be synthesized by cycloaddition of benzothiete (1) and aromatic nitroso compounds 3. The regioselectivity of the primary step and the secondary thermal or acid-catalyzed rearrangements are discussed.
Diels-Alder Reactions of (1H-Indol-3-yl)-enacetamides and -endiacetamides: A Selective Access to Acetylamino-Functionalized [b]Annelated Indoles and …
1991
Diels-Alder reactions of the (1H-indol-3-yl)-enacetamides and -endiacetamides 1a–d with some carbodieno-philes and 4-phenyl-3H-1,2,4-triazole-3,5(4H)-dione give rise to the novel amino-functionalized carbazole; 4–6 and 8 (Scheme 3). Ethenetetracarbonitrile reacts with 1b to furnish the Michael-type adduct 7 (Scheme 3). Structural aspects of the starting materials 1, which exhibit above all 3-vinyl-1H-indole reactivity, are discussed with regard to the prediction of a Diels-Alder process.
A Synthetic Model for the [4+2] Cycloaddition in the Biosynthesis of the Brevianamides, Paraherquamides, and Related Compounds
2000
Abstract The reactivity of model systems for the proposed [4+2] cycloaddition in the biosynthesis of the brevianamides, paraherquamides, and marcfortines is explored. The model for the intermolecular reaction reveals that the cycloaddition takes place under mild conditions only if activated, very reactive dienophiles are used. When relatively unreactive dienophiles such as cyclopentene and cyclohexene are used, harsh reaction conditions and/or a Lewis acid catalyst are necessary for the reaction. In contrast, the model for the intramolecular reaction demonstrates that the cycloaddition takes place within a few hours at room temperature, even in the absence of a Lewis acid catalyst. Conclusi…
Regio- and Stereoselective Synthesis of Spiropyrrolizidines and Piperazines through Azomethine Ylide Cycloaddition Reaction.
2015
A series of original spiropyrrolizidine derivatives has been prepared by a one-pot three-component [3 + 2] cycloaddition reaction of (E)-3-arylidene-1-phenyl-pyrrolidine-2,5-diones, l-proline, and the cyclic ketones 1H-indole-2,3-dione (isatin), indenoquinoxaline-11-one and acenaphthenequinone. We disclose an unprecedented isomerization of some spiroadducts leading to a new family of spirooxindolepyrrolizidines. Furthermore, these cycloadducts underwent retro-1,3-dipolar cycloaddition yielding unexpected regioisomers. Upon treatment of the dipolarophiles with in situ generated azomethine ylides from l-proline or acenaphthenequinone, formation of spiroadducts and unusual polycyclic fused pip…