Bent Pyrenes: Springboards to Aromatic Belts?

Bodwell, Graham J.; Venkataramana, Gandikota; Sagar, Unikela Kiran

doi:10.1002/9781118011263.ch14

Cited by 5 publications

(3 citation statements)

References 45 publications

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“…Among the vast number of cyclophanes prepared so far, pyrene-based cyclophanes, also known as pyrenophanes, have attracted much attention recently . This is due to not only the extraordinary photophysical and photochemical properties of this particular polycyclic aromatic hydrocarbon but also its importance as a key structural unit for the preparation of large curved π-organic materials. , For these reasons, a good number of pyrenophanes having (1,3), (1,6), (1,7), (1,8), (2,4), (2,7), and (4,9) bridging motifs have been prepared and fully characterized . However, although considerable efforts toward the synthesis and structural analyses of these compound have been made, , their chemistry remains comparatively underdeveloped.…”

Section: Introductionmentioning

confidence: 99%

“…This is due to not only the extraordinary photophysical and photochemical properties of this particular polycyclic aromatic hydrocarbon but also its importance as a key structural unit for the preparation of large curved π-organic materials. , For these reasons, a good number of pyrenophanes having (1,3), (1,6), (1,7), (1,8), (2,4), (2,7), and (4,9) bridging motifs have been prepared and fully characterized . However, although considerable efforts toward the synthesis and structural analyses of these compound have been made, , their chemistry remains comparatively underdeveloped. Thus, only a few reactions including Diels–Alder cycloadditions, , and some unusual processes involving t -BuLi and alkali metals, have been reported so far.…”

Section: Introductionmentioning

confidence: 99%

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Factors Governing the Diels–Alder Reactivity of (2,7)Pyrenophanes

García-Rodeja

Fernández

2017

J. Org. Chem.

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The physical factors governing the Diels-Alder reactivity of (2,7)pyrenophanes have been computationally explored using state-of-the-art Density Functional Theory calculations. It is found that the [4 + 2]-cycloaddition reactions between these cyclophanes and tetracyanoethylene, which occur concertedly through highly asynchronous transition states, proceed with lower activation barriers and are more exothermic than the analogous process involving the parent planar pyrene. The influence of the bent equilibrium geometry of the pyrenophane as a function of the length of the bridge as well as the nature of the tether on the transformation are analyzed in detail. By means of the Activation Strain Model of reactivity and the Energy Decomposition Analysis methods, a detailed quantitative understanding of the reactivity of this particular family of cyclophanes is presented.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Factors Governing the Diels–Alder Reactivity of (2,7)Pyrenophanes

García-Rodeja

Fernández

2017

J. Org. Chem.

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“…In this context, they used strained pyrene derivative, i.e. [7](2,7)pyrenophane 53b, 25 to encourage a more exothermic reaction with a lower activation energy. As suggested by DFT calculations that clarified the lower relative energies of the cycloadducts (ΔG = -0.1 and -8.3 kcal/mol, ΔG ‡ = ca.…”

Section: Two-step Aza-apex Reaction Using a Polycyclic Azomethine Ylidementioning

confidence: 99%

Heteroatom-Embedding Annulative π-Extension (Hetero-APEX) Reactions: An Overview

Ito,

Itami,

Kawahara

2023

Synthesis

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Heteroatom-embedded polycyclic aromatic compounds (hetero-PACs) are a class of organic compounds contributing to a variety of research fields such as materials science, chemical biology and so on. For applications using hetero-PACs, efficient preparation of hetero-PACs is essential. In particular, reactions transforming unfunctionalized aromatic compounds to hetero-PACs using appropriate heteroatom-containing aromatic compounds (π-extending agents) represent the most ideal way to prepare hetero-PACs. In this review, such heteroatom-embedding annulative π-extension (hetero-APEX) reactions including their reaction mechanisms and scope of substrates are described.

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Synthesis of a π‐Extended Azacorannulenophane Enabled by Strain‐Induced 1,3‐Dipolar Cycloaddition

et al. 2022

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The first example of a cyclophane bearing a nitrogen-containing buckybowl was synthesized via sequential 1,3-dipolar cycloaddition and palladium-catalyzed intramolecular cyclization. The key to the successful synthesis is the strain-induced 1,3-dipolar cycloaddition of a polycyclic aromatic azomethine ylide to the K-region of [7](2,7)pyrenophane. The resulting π-extended azacorannulenophane exhibits intriguing structural and physical properties, including unique variation of bowl depth, extraordinarily high-field chemical shifts in its 1 H NMR spectrum, a decreased HOMO-LUMO gap, and a red shift in the absorption/emission spectrum, when compared to those of the parent azacorannulene. These characteristics are derived from both the πextension to the polycyclic aromatic system in the cyclophane structure and the increased curvature enforced by the seven-carbon aliphatic chain.

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Bent Pyrenes: Springboards to Aromatic Belts?

Cited by 5 publications

References 45 publications

Factors Governing the Diels–Alder Reactivity of (2,7)Pyrenophanes

Factors Governing the Diels–Alder Reactivity of (2,7)Pyrenophanes

Heteroatom-Embedding Annulative π-Extension (Hetero-APEX) Reactions: An Overview

Synthesis of a π‐Extended Azacorannulenophane Enabled by Strain‐Induced 1,3‐Dipolar Cycloaddition

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