1,2,3- versus 1,2-Indeno Ring Fusions Influence Structure Property and Chirality of Corannulene Bowls

Shi, Liyi; Roch, Loı̈c M.; Allemann, Oliver; Xu, Jun; Vanthuyne, Nicolas; Baldridge, Kim K.; Siegel, Jay S.

doi:10.1021/acs.joc.8b00320

Cited by 12 publications

(6 citation statements)

References 48 publications

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“…450 Biaryl substrates with an aliphatic ortho-substituent (Me, iPr, and tBu) can undergo a competitive reaction pathway by an unusual electrophilic substitution of a C(sp 3 )−H bond by the phenyl cation (Scheme 113). 451,452 Exclusive cyclization involving C(sp 3 )−H bond insertion is seen in those cases where the S E Ar reaction would form a strained ring (e.g., 301b → 324 and 301c → 325).…”

Section: Silylium-ion-promoted Deoxygenation and Hydrosilylation Reac...mentioning

confidence: 99%

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

et al. 2021

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The history of silyl cations has all the makings of a drama but with a happy ending. Being considered reactive intermediates impossible to isolate in the condensed phase for decades, their actual characterization in solution and later in solid state did only fuel the discussion about their existence and initially created a lot of controversy. This perception has completely changed today, and silyl cations and their donor-stabilized congeners are now widely accepted compounds with promising use in synthetic chemistry. This review provides a comprehensive summary of the fundamental facts and principles of the chemistry of silyl cations, including reliable ways of their preparation as well as their physical and chemical properties. The striking features of silyl cations are their enormous electrophilicity and as such reactivity as super Lewis acids as well as fluorophilicity. Known applications rely on silyl cations as reactants, stoichiometric reagents, and promoters where the reaction success is based on their steady regeneration over the course of the reaction. Silyl cations can even be discrete catalysts, thereby opening the next chapter of their way into the toolbox of synthetic methodology.

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Section: Silylium-ion-promoted Deoxygenation and Hydrosilylation Reac...mentioning

confidence: 99%

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

et al. 2021

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“…Distorted polycyclic aromatic hydrocarbons (PAHs) bearing a curved π-surface are considered as complements to planar PAHs and have received much attention . The highly strained structures of distorted PAHs endow them with intriguing properties, including chirality, supramolecular assembly, and electronic conductivity, leading to much exploration on semiconductor materials, , fullerene separation, and bioimagings . Corannulene is regarded as an ideal precursor for developing π-extended PAHs, because of its unique structural properties.…”

mentioning

confidence: 99%

Tuning the Properties of Corannulene-Based Polycyclic Aromatic Hydrocarbons by Varying the Fusing Positions of Corannulene

Wang

Zhao

et al. 2020

Org. Lett.

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The selective fusions with pyrene derivative to the rim and flank bonds of corannulene generated 4 and 7, respectively, which underwent a Scholl reaction to provide novel distorted PAHs CORA-1 and CORA-2, consisting of corannulene and dibenzocoronene units with different connections between them. The studies revealed that the properties of these PAHs are highly dependent on the fusing positions of corannulene.

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“…Baldridge and Siegel reported a trio of annulated corannulenes (Fig. 5c) 42 . 1,6-dibromo-2,5-dimethylcorannulene 58 is coupled with 2-fluoro-phenyl boronic acid and 2-chloro-phenyl boronic acid to give 59a (X = Cl) and 59b (X = F) respectively.…”

Section: Reactions Involving Metal Catalysismentioning

confidence: 97%

Synthesis of corannulene-based nanographenes

2019

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Corannulene (C 20 H 10) is a polycyclic hydrocarbon in which five six-membered rings surround a central five-membered ring to construct a bowl-like aromatic structure. Here we examine the development of synthetic strategies that allow for the growth of the peripheral aromatic rings as a means to extend the aromatic area of the central corannulene nucleus and provide access to unique nanocarbon molecules. s p 2-hybridised structures of carbon have fascinated the research community for a very long time. In 1985, buckminsterfullerene, otherwise known as C 60 , was discovered (Fig. 1a) 1. In this ball-shaped molecule, the curvature in the structure stems from the presence of fivemembered rings. In 1991, carbon nanotubes arrived on the scene 2. Here, the structure is cylindrical and composed of only rolled-up six-membered rings. In 2004, a sheet-like single layer from graphite-graphene-was isolated 3. All of these materials were shown to have extraordinary electronic and mechanical properties due to their unique curved or planar sp 2-hybridised aromatic structures. Inspired by these discoveries, chemists have been developing strategies to access such aromatic hydrocarbons through rational ('bottom-up') synthetic approaches. Scott's 12-step chemical synthesis of fullerene C 60 from a rationally designed precursor is a testament to the ingenuity and resourcefulness of organic chemists 4. In planar structures, nanographenes (well-defined cutouts of graphene with nano-scale dimensions) can now be prepared on a regular basis with a very diverse portfolio 5. It is expected that combining the planar structure of graphene with the curvature of fullerenes may produce hybrid materials with interesting properties 6-8. To induce non-planarity into nanographenes, a practical approach would be to introduce a fivemembered ring such as in the case of fullerene, C 60. A perfect building block that allows for such a structural arrangement to happen is corannulene (1)-a molecule in which five six-membered rings surround a central five-membered ring to give a bowl-like structure (Fig. 1b) 9-20. Corannulene also offers many beneficial features as a molecular building block. It has high solubility in common organic solvents. It can be derivatized in a well-defined manner. Due to synthetic ease, the derivatives can be prepared on a multigram scale. These attributes are important as they allow for the scalable preparation of carefully designed corannulene-based building blocks and the subsequent synthesis, purification and structural analysis of the larger (fused) aromatic systems. Recently, therefore, there has been a surge in employment of corannulene as a core molecule in the synthesis of extended aromatic structures. Our aim in this review article is to discuss

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1,2,3- versus 1,2-Indeno Ring Fusions Influence Structure Property and Chirality of Corannulene Bowls

Cited by 12 publications

References 48 publications

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts

Tuning the Properties of Corannulene-Based Polycyclic Aromatic Hydrocarbons by Varying the Fusing Positions of Corannulene

Synthesis of corannulene-based nanographenes

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