Trefoil‐Shaped Porous Nanographenes Bearing a Tribenzotriquinacene Core by Three‐fold Scholl Macrocyclization

He, Lisi; Ng, Chun-Fai; Li, Yuke; Liu, Zhifeng; Kuck, Dietmar; Chow, Hak‐Fun

doi:10.1002/ange.201808461

“…Tr ibenzotriquinacene,w ith au nique bowl-shape framework, is an interesting building block for macromolecular construction. [9] Thec hirality of these building blocks may have ac rucial effect on the determination of the shape of the macromolecule.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…Theu se of chiral chromatography is required to obtain the enantiomerically enriched isomer. [8] Theb owlshaped molecules tribenzotriquinacenes, [9] building blocks used in host/guest supramolecular materials,n eed chiral resolutions to get the optically enriched enantiomers after the racemic forms are synthesized. [10] Another example is the natural product fredericamycin A( Figure 1a).…”

mentioning

confidence: 99%

Carbene‐Catalyzed Desymmetrization and Direct Construction of Arenes with All‐Carbon Quaternary Chiral Center

Zhu

¹

,

Liu

²

,

Smetankova

³

et al. 2019

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Multisubstituted arenes such as indanes with attached all-carbon quaternary centers are unique scaffolds in synthetic functional molecules and sophisticated natural products.Akey challenge in preparing such molecules lies in the enantioselective installation of the quaternary carbon centers.C onventional methods in this direction include asymmetric substitution reactions and substrate-controlled cyclization reactions.T hese reactions lead to poor stereoselectivities and/or require long and tedious synthetic steps.Disclosed here is ao ne-step organic catalytic strategy for enantioselective access to this class of molecules.T he reaction involves an Nheterocyclic carbene catalyzedp rocess for direct benzene construction, indane formation, remote-carbon desymmetrization, and excellent chirality control. This approach will enable the concise synthesis of arene-containing molecules,i ncluding those with complex structures and challenging chiral centers.

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“…(product 3x). [9] Thec hirality of these building blocks may have ac rucial effect on the determination of the shape of the macromolecule. Ther eactions all proceeded smoothly and gave the desired spirocyclic indanes in good yields (Scheme 1, products 3y-y2).…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[4] Among the molecules containing arenes with chiral centers,i ndane derivatives having an all-carbon quaternary chiral center (Figure 1a)a re particularly difficult to make in optically enriched forms. [8] Theb owlshaped molecules tribenzotriquinacenes, [9] building blocks used in host/guest supramolecular materials,n eed chiral resolutions to get the optically enriched enantiomers after the racemic forms are synthesized. Theu se of chiral chromatography is required to obtain the enantiomerically enriched isomer.…”

mentioning

confidence: 99%

Carbene‐Catalyzed Desymmetrization and Direct Construction of Arenes with All‐Carbon Quaternary Chiral Center

Zhu

¹

,

Liu

²

,

Smetankova

³

et al. 2019

View full text Add to dashboard Cite

Multisubstituted arenes such as indanes with attached all-carbon quaternary centers are unique scaffolds in synthetic functional molecules and sophisticated natural products.Akey challenge in preparing such molecules lies in the enantioselective installation of the quaternary carbon centers.C onventional methods in this direction include asymmetric substitution reactions and substrate-controlled cyclization reactions.T hese reactions lead to poor stereoselectivities and/or require long and tedious synthetic steps.Disclosed here is ao ne-step organic catalytic strategy for enantioselective access to this class of molecules.T he reaction involves an Nheterocyclic carbene catalyzedp rocess for direct benzene construction, indane formation, remote-carbon desymmetrization, and excellent chirality control. This approach will enable the concise synthesis of arene-containing molecules,i ncluding those with complex structures and challenging chiral centers. Figure 1. Arenes bearing challenging chiral centers.

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“…Curved aromatic molecules have found diverse uses in supramolecular and nanomaterials chemistry. 1 − 3 In particular, carbon-rich cavities of such systems have been used to develop cylindrical, 3 − 11 concave, 12 , 13 and macrocyclic hosts 14 , 15 for spherical guest molecules and ions, self-assembling surfaces, 16 , 12 , 17 and porous organic materials. 18 , 19 In these systems, the receptor function can be precisely controlled by the type and extent of curvature and by adjusting the cavity dimensions.…”

Section: Introductionmentioning

confidence: 99%

Feeding a Molecular Squid: A Pliable Nanocarbon Receptor for Electron-Poor Aromatics

Frydrych

¹

,

Lis

²

,

Bury

³

et al. 2020

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A hybrid nanocarbon receptor consisting of a calix[4]arene and a bent oligophenylene loop (“molecular squid”), was obtained in an efficient, scalable synthesis. The system contains an electron-rich cavity with an adaptable shape, which can serve as a host for electron deficient guests, such as diquat, 10-methylacridinium, and anthraquinone. The new receptor forms inclusion complexes in the solid state and in solution, showing a dependence of the observed binding strength on the shape of the guest species and its charge. The interaction with the methylacridinium cation in solution was interpreted in terms of a 2:1 binding model, with K 11 = 5.92(7) × 10 3 M –1 . The solid receptor is porous to gases and vapors, yielding an uptake of ca. 4 mmol/g for methanol at 293 K. In solution, the receptor shows cyan fluorescence (λ max em = 485 nm, Φ F = 33%), which is partly quenched upon binding of guests. Methylacridinium and anthraquinone adducts show red-shifted emission in the solid state, attributable to the charge-transfer character of these inclusion complexes.

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Trefoil‐Shaped Porous Nanographenes Bearing a Tribenzotriquinacene Core by Three‐fold Scholl Macrocyclization

Cited by 14 publications

References 65 publications

Carbene‐Catalyzed Desymmetrization and Direct Construction of Arenes with All‐Carbon Quaternary Chiral Center

Carbene‐Catalyzed Desymmetrization and Direct Construction of Arenes with All‐Carbon Quaternary Chiral Center

Carbene‐Catalyzed Desymmetrization and Direct Construction of Arenes with All‐Carbon Quaternary Chiral Center

Feeding a Molecular Squid: A Pliable Nanocarbon Receptor for Electron-Poor Aromatics

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