Inherently chiral concave molecules—from synthesis to applications

Szumna, Agnieszka

doi:10.1039/b919527k

Cited by 215 publications

(159 citation statements)

References 73 publications

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“…Sumanene has a partial structure of fullerenes [1,2], offering a lot of opportunities compared to these structures. Although the synthesis, structural characterization, and complexation of buckybowls have been studied for more than 15 years [1,[3][4][5][6][7][8] there is still a lot of space for theoretical research of potential application of these structures in the various fields of science.…”

Section: Introductionmentioning

confidence: 99%

Aromaticity, response, and nonlinear optical properties of sumanene modified with boron and nitrogen atoms

2014

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We investigated the effects of substitution on the sumanene benzylic CH2 groups with BH and NH groups using density functional theory computations. Our study shows that various properties of sumanene could be finely tuned for the application in the areas closely related to the materials science. Structural properties are significantly altered with such modifications and other properties as well. Charge distributions were evaluated through natural population analysis (NPA), while stability of investigated structures was investigated using quantum molecular descriptors. Using molecular orbital analysis further insight into the effects of substitution was obtained. Potential of sumanene as a candidate for application in the field of organic electronics is assessed through calculations of exciton binding energy. Non-linear optical properties of investigated structures were investigated using the first hyperpolarizability tensor. Special attention was paid to the aromaticity of sumanene. This property was evaluated employing NICS parameter while for detailed study of obtained results we used NBO and NBOdel analysis.

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Section: Introductionmentioning

confidence: 99%

Aromaticity, response, and nonlinear optical properties of sumanene modified with boron and nitrogen atoms

2014

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“…Therefore, by selective ipso-nitration, the resultant mononitrocalix [4]arene 2 and trinitrocalix [4]arene 4 would be inherently chiral calixarenes (Scheme 1), which would be one of the most concise methods for synthesis of this class of chiral calixarenes. However, while inherently chiral calixarenes usually exhibit excellent properties in chiral recognition, the synthesis of them is generally difficult and needs complex reaction route [25][26][27][28][29][30].…”

Section: Resultsmentioning

confidence: 99%

Selective nitration of calix[4]arenes that easily gave inherently chiral calix[4]arenes

Wang

Chen

Zheng

et al. 2014

J Incl Phenom Macrocycl Chem

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Proximally dietherified calix[4]arene at lower rim was selectively nitrated to give mononitrocalix[4]arene, dinitrocalix[4] arene, and trinitrocalix[4]arene,respectively, under different reaction conditions. These three nitrocalix[4]arenes could be purified in good yield just by recrystallization, which provided a concise approach to inherently chiral calixarene. It was disclosed by crystal structure of trinitrocalix[4]arene that R-enantiomer and S-enantiomer of it could form a self-included dimer by NO 2 -HAr hydrogen bond and CH 3 -Pi interaction in the cavity of the calixarene. In the presence of optically pure (1S,2S)-1,2-diphenyl-1,2-ethanediamine, (1R,2R)-1,2-cyclohexanediamine, cinchonidine, or cinchonine, the two enantiomers of trinitrocalix[4]arene could be discriminated by 1 H NMR spectrum.

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“…[3,4] Especially,t he bowl-shaped structured ue to the central four-coordinate boron atom is one of the attractive properties, because a bowl-shaped structure leads to two different curved p surfaces (convexa nd concave surfaces) and ab owl chirality. [5] Ab owl inversion is an important phenomenon for bowl-shaped molecules, because it influences key properties in ad ynamic sense and causes the inversion of the chiralityf or bowl-chiral molecules. Therefore, bowl-inversion dynamics have been widely studied.…”

Section: Introductionmentioning

confidence: 99%

Observation of Diastereomeric Interconversions of β‐Sulfinylsubporphyrins as Evidence for Bowl Inversion

Yoshida

Osuka

2015

Chemistry A European J

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B-Methoxy β-(4-methoxyphenylsulfinyl)subporphyrin and B-phenyl β-(4-methoxyphenylsulfinyl)subporphyrin were synthesized by oxidation of the corresponding β-sulfanylsubporphyrins with m-chloroperbenzoic acid and were separated into diastereomers, respectively. B-Methoxy subporphyrin diastereomers were interconverted to each other in methanol or ethanol, whereas such interconversion was not observed for B-phenyl subporphyrin diastereomers even at high temperature. Diastereomeric interconversions of B-methoxy subporphyrins were dramatically accelerated by addition of trifluoroacetic acid. These results suggest that the diastereomeric interconversions of B-methoxy subporphyrins, namely, their bowl inversions, proceed via a mechanism involving protonation-induced generation of subporphyrin borenium cations followed by nucleophilic attacks by alcohols.

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Inherently chiral concave molecules—from synthesis to applications

Cited by 215 publications

References 73 publications

Aromaticity, response, and nonlinear optical properties of sumanene modified with boron and nitrogen atoms

Aromaticity, response, and nonlinear optical properties of sumanene modified with boron and nitrogen atoms

Selective nitration of calix[4]arenes that easily gave inherently chiral calix[4]arenes

Observation of Diastereomeric Interconversions of β‐Sulfinylsubporphyrins as Evidence for Bowl Inversion

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