Vermittlung organischer Reaktionen durch nichtbenzoide carbocyclische aromatische Ionen

Tropylium bromide undergoes noncatalyzed, regioselective additions to al arge variety of Michael acceptors.I n this way, acrylic esters are converted into b-bromo-a-cycloheptatrienylpropionic esters.T he reactions are interpreted as nucleophilic attacko fb romide ions at the electron-deficient olefins and the approach of the tropylium ion to the incipient carbanion. Quantum chemical calculations were performed to elucidate the analogy to the amine-or phosphine-catalyzed Rauhut-Currier reactions.S ubsequent synthetic transformations of the bromo-cycloheptatrienylated adducts are reported.

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Halide Anion Triggered Reactions of Michael Acceptors with Tropylium Ion

Hussein

Tran

Huynh

et al. 2019

Angewandte Chemie

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Self‐Assembly of Aminocyclopropenium Salts: En Route to Deltic Ionic Liquid Crystals

et al. 2020

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Aminocyclopropenium ions have raised much attention as organocatalysts and redox active polymers. However, the self‐assembly of amphiphilic aminocyclopropenium ions remains challenging. The first deltic ionic liquid crystals based on aminocyclopropenium ions have been developed. Differential scanning calorimetry, polarizing optical microscopy and X‐ray diffraction provided insight into the unique self‐assembly and nanosegregation of these liquid crystals. While the combination of small headgroups with linear p‐alkoxyphenyl units led to bilayer‐type smectic mesophases, wedge‐shaped units resulted in columnar mesophases. Upon increasing the size and polyphilicity of the aminocyclopropenium headgroup, a lamellar phase was formed.

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Conformation and Aromaticity Switching in a Curved Non‐Alternant sp² Carbon Scaffold

2020

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A curved sp 2 carbon scaffold containing fused pentagon and heptagon units (1) was synthesized by Pdcatalyzed [5+2] annulation from a 3,9-diboraperylene precursor and shows two reversible oxidation processes at low redox potential, accompanied by a butterfly-like motion. Stepwise oxidation produced radical cation 1C + and dication 1 2+. In the crystal structure, 1 exhibits a chiral cisoid conformation and partial p-overlap between the enantiomers. For the radical cation 1C + , a less curved cisoid conformation is observed with a p-dimer-type arrangement. 1 2+ adopts a more planar structure with transoid conformation and slip-stacked p-overlap with closest neighbors. We also observed an intermolecular mixed-valence complex of 1•(1C +) 3 that has a huge trigonal unit cell [(1) 72 (SbF 6) 54 •(hexane) 101 ] and hexagonal columnar stacks. In addition to the conformational change, the aromaticity of 1 changes from localized to delocalized, as demonstrated by AICD and NICS(1) zz calculations.

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Vermittlung organischer Reaktionen durch nichtbenzoide carbocyclische aromatische Ionen

Abstract: Schema 1. Synthese dikationischer Ether nach Stang. Schema 2. Studie der Reaktionz wischen Tropyliumbromid und tert-Butylalkohol von Parnes. Schema 3. Anellierte Furopyrimidin-Tropylium-Ionen vermitteln NAD + / NADH-artige Redoxreaktionen.

Cited by 10 publications

References 89 publications

Halide Anion Triggered Reactions of Michael Acceptors with Tropylium Ion

Halide Anion Triggered Reactions of Michael Acceptors with Tropylium Ion

Self‐Assembly of Aminocyclopropenium Salts: En Route to Deltic Ionic Liquid Crystals

Conformation and Aromaticity Switching in a Curved Non‐Alternant sp² Carbon Scaffold

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Vermittlung organischer Reaktionen durch nichtbenzoide carbocyclische aromatische Ionen

Abstract: Schema 1. Synthese dikationischer Ether nach Stang. Schema 2. Studie der Reaktionz wischen Tropyliumbromid und tert-Butylalkohol von Parnes. Schema 3. Anellierte Furopyrimidin-Tropylium-Ionen vermitteln NAD + / NADH-artige Redoxreaktionen.

Cited by 10 publications

References 89 publications

Halide Anion Triggered Reactions of Michael Acceptors with Tropylium Ion

Halide Anion Triggered Reactions of Michael Acceptors with Tropylium Ion

Self‐Assembly of Aminocyclopropenium Salts: En Route to Deltic Ionic Liquid Crystals

Conformation and Aromaticity Switching in a Curved Non‐Alternant sp2 Carbon Scaffold

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Conformation and Aromaticity Switching in a Curved Non‐Alternant sp² Carbon Scaffold