Topic
Norbornadiene
About: Norbornadiene is a research topic. Over the lifetime, 2389 publications have been published within this topic receiving 38603 citations.
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18 citations
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TL;DR: In this article, the electron transfer from the sensitizer, intersystem crossing of resultant radical-ion pairs, and ion recombination were used to give norbornadiene triplets followed by rearrangement to the valence isomer.
Abstract: Quenching of the fluorescence of a series of electron donor aromatic hydrocarbons in acetonitrile by dimethyl bicyclo(2.2.1)hepta-2,5-diene-2,3-dicarboxylate results in isomerization of the norbornadiene with varying efficiency. Quantum yield, CIDNP, and flash photolysis results are consistent with a rearrangement mechanism involving electron transfer from the sensitizer, intersystem crossing of resultant radical-ion pairs, and ion recombination to give norbornadiene triplets followed by rearrangement to the valence isomer. Where energetic factors are favorable, the isomerization quantum yield is as high as 0.39 and the efficiency of formation of norbornadiene triplets via ion recombination as high as 65%.
18 citations
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TL;DR: In this article, it was concluded that the previous claim of the synthesis of methanoisobenzofuran derivatives was incorrect, and the p-tolylmethanoisoindole reacted with dimethyl acetylenedicarboxylate to give a novel 1 : 3 adduct.
Abstract: 2-Phenyl- and 2-(p-tolyl)-4,7-dihydro-4,7-methano-2H-isoindole were synthesized by treatment of 3-(diethoxymethyl)bicyclo[2.2.1]hepta-2,5-diene-2-carbaldehyde with aniline or p-toluidine, followed by reduction with sodium borohydride and acid-catalyzed cyclization. It was concluded that the previous claim of the synthesis of methanoisoindole derivatives was incorrect. 4,7-Dihydro-4,7-methanoisobenzofuran was prepared by the reduction of the norbornadiene-monocarbaldehyde with sodium borohydride and subsequent treatment with Amberlyst-15. The p-tolylmethanoisoindole reacted with dimethyl acetylenedicarboxylate to give a novel 1 : 3 adduct. On the other hand, in the reaction of the methanoisobenzofuran with N-phenylmaleimide, spontaneous oxidation of the Diels–Alder cycloadduct took place to give exclusively its epoxide.
18 citations
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TL;DR: The reactivity of the double bonds in substituted benzonorbornadienes was analyzed by determination of the pyramidalization angles and the relative energies of various carbenes and their rearrangement to allene were studied at B3LYP/6-31G(d) level.
Abstract: For the synthesis of endo-configured cyclopropylidenes annelated to benzonorbornadiene, first the exo-bridge hydrogen in benzonorbornadiene was blocked with ethyl, bromine, and methoxy groups. All efforts to add dichloro-, dibromo-, or fluorobromocarbenes to ethylbenzonorbornadiene failed. However, addition of fluorobromocarbene to bromo- or methoxybenzonorbornadiene gave the corresponding cyclopropane derivatives bearing two halogen atoms, which were submitted to the Doering−Moore−Skattebol reaction. The formed allene intermediates were trapped with furan. The reactivity of the double bonds in substituted benzonorbornadienes was analyzed by determination of the pyramidalization angles. Furthermore, the relative energies of various carbenes and their rearrangement to allene were studied at B3LYP/6-31G(d) level.
18 citations
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TL;DR: In this article, the feasibility of doubly bridged ansa-zirconocenes based on the norbornadiene skeleton was investigated by molecular mechanics analysis on models of catalytic intermediates corresponding to the monomer coordination step as well as on the pseudotransition states relative to the possible monomer insertion reaction.
18 citations