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1.
Jing He Mohan Yu Maofu Pang Yanqing Fan Zhe Lian Dr. Ying Wang Prof. Wenguang Wang Prof. Yajun Liu Prof. Hua Jiang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(13):e202103832
Structural designs combining cycloparaphenylenes (CPPs) backbone with planar chiral [2.2]paracyclophane ([2.2]PCP) lead to optical-active chiral macrocycles with intriguing properties. X-ray crystal analysis revealed aesthetic necklace-shaped structures and size-dependent packages with long-range channels. The macrocycles exhibit unique photophysical properties with high fluorescence quantum yield of up to 82 %, and the fluorescent color varies with ring size. In addition, size-dependent chiroptical properties with moderately large CPL dissymmetry factor of 10−3 and CPL brightness in the range of 30–40 M−1 cm−1 were observed. 相似文献
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New Types of Planar Chiral [2.2]Paracyclophanes and Construction of One‐Handed Double Helices 下载免费PDF全文
Prof. Yasuhiro Morisaki Risa Sawada Dr. Masayuki Gon Prof. Yoshiki Chujo 《化学:亚洲杂志》2016,11(18):2524-2527
New types of planar chiral (Rp)‐ and (Sp)‐4,7,12,15‐tetrasubstituted [2.2]paracyclophanes were synthesized from racemic 4,12‐dihydroxy[2.2]paracyclophane as the starting compound. Regioselective dibromination and transformation afforded a series of planar chiral (Rp)‐ and (Sp)‐4,7,12,15‐tetrasubstituted [2.2]paracyclophanes, which can be used as chiral building blocks. In this study, left‐ and right‐handed double helical structures were constructed via chemoselective Sonogashira–Hagihara coupling. The double helical compounds were excellent circularly polarized luminescence (CPL) emitters with large molar extinction coefficients, good photoluminescence quantum efficiencies, and large CPL dissymmetry factors. 相似文献
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Katsuaki Kikuchi Jun Nakamura Yuuya Nagata Hiromu Tsuchida Takahiro Kakuta Tomoki Ogoshi Yasuhiro Morisaki 《化学:亚洲杂志》2019,14(10):1681-1685
Planar chiral building blocks based on 4,7,12,15‐tetrasubstituted [2.2]paracyclophanes were obtained via a synthetic route involving an optical resolution step. Planar chiral enantiomers, comprising two fluorophores that were stacked to form a V‐shaped higher‐ordered structure, were synthesized from these building blocks. The V‐shaped molecules emitted intense circularly polarized luminescence (CPL). Their chiroptical properties were compared with those of X‐shaped molecules bearing the same two fluorophores stacked together. The CPL sign of the X‐shaped molecule was opposite to that of the V‐shaped molecule, which is supported by the theoretical results, indicating that the CPL sign can be controlled by the orientation of the stacked fluorophores. 相似文献
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V. A. Nikanorov V. G. Kharitonov E. V. Yatsenko D. P. Krut'ko M. V. Galakhov S. O. Yakushin V. V. Mikul'shina V. I. Rozenberg V. N. Guryshev V. P. Yur'ev O. A. Reutov 《Russian Chemical Bulletin》1992,41(8):1430-1434
From the reaction mixtures in the uncatalyzed polybromination of [2.2]paracyclophane by the action of excess Br2 in CCl4, there have been found along with the known products — 4,15- and 4,16-dibromo[2.2]paracyclophanes — two new aromatic tribromides of this series, which have been isolated in pure form: 4,12,15- and 4,15,16-tribromo[2.2]paracyclophanes. Special experiments demonstrated that the mixtures of these tribromides are formed as a result of competitive monobromination of 4,15-dibromo[2.2]paracyclophane; the 4,15,16-tribromo[2.2]paracyclophane, together with still another newly isolated isomer of this series — 4,8,12-tribromo[2.2]paracyclophane — is formed as a result of competitive monobromination of 4,16-dibromo[2.2]paracyclophane. As an explanation of the features of the orienting effect of substituents in these competing reactions, a rule was proposed: On the conventional orientation (from the electronic point of view) of entry of the bromine atom into the substituted ring (para > ortho > meta), a steric limitation is imposed on its attack in the pseudo-gem-position, owing to the bulky bromine atom that is transannularly positioned above it in the neighboring aromatic ring. The structures of all of the tribromides were established on the basis of elemental analyses, mass spectrometry, and1H NMR spectrometry (including PMR using the homonuclear Overhauser effect). The data obtained in this work indicate that the 4,12,15-tribromo[2.2]paracyclophane and 4,15,16-tribromo[2.2]paracyclophane are predecessors of the two tetrabromides previously obtained by Cram — 4,7,12,15- and 4,5,15,16-tetrabromo[2.2]paracyclophanes; and the 4,8,12-tribromo[2.2]paracyclophane is a possible predecessor of 4,8,12,16-tetrabromo[2.2]paracyclophane, which is unknown up to the present time.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1837–1843, August, 1992. 相似文献
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Abstract Several novel flexibility-restricted imidazo[1,5-a]pyridinium triflates (abbreviated as imidazolium salts) were synthesized from (4S p,13R p)-(?)-4-amino-13-bromo[2.2]paracyclophane and pyridylaldehyde. These imidazolium salts can be used as nitrogen-containing heterocyclic carbene precursors in asymmetric catalysis and here they are applied in the Rh-catalyzed asymmetric 1,2-addition of arylboronic acids to aldehydes. After optimizing the catalytic situations and testing a series of substrates, moderate enantioselectivity and good yield were obtained. 相似文献
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4,16-Dibromo[2.2]paracyclophane (4) is isomerised to 4,12-dibromo[2.2]paracyclophane (1) by the application of microwaves in DMF solution. 相似文献
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Jin‐Fa Chen Xiaodong Yin Bowen Wang Kai Zhang Guoyun Meng Songhe Zhang Yafei Shi Nan Wang Suning Wang Pangkuan Chen 《Angewandte Chemie (International ed. in English)》2020,59(28):11267-11272
Enantiopure molecules based on macrocyclic architecture are unique for applications in enantioselective host‐guest recognition, chiral sensing and asymmetric catalysis. Taking advantage of the chiral transfer from the intrinsically planar chirality of pillar[5]arenes, we herein present an efficient and straightforward approach to achieve early examples of highly luminescent chiral systems ( P5NN and P5BN ). The optical resolution of their enantiomers has been carried out via preparative chiral HPLC, which was ascribed to the molecular functionalization of pillar[5]arenes with π‐conjugated, sterically bulky triarylamine (Ar3N) as an electron donor and triarylborane (Ar3B) as an acceptor. This crucial design enabled investigations of the chiroptical properties, including circular dichroism (CD) and circularly polarized luminescence (CPL) in the solid state. The intramolecular charge transfer (ICT) nature in P5BN afforded an interesting thermochromic shift of the emission over a wide temperature range. 相似文献
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Rozenberg V. I. Sergeeva E. V. Kharitonov V. G. Vorontsova N. V. Vorontsov E. V. Mikul'shina V. V. 《Russian Chemical Bulletin》1994,43(6):1018-1023
The cross-coupling reactions of 4-bromo[2.2]paracyclophane withp-tolylmagnesium bromide in the presence of various palladium and nickel complexes have been studied. It was found that [1,1 -bis(diphenylphosphinoferrocene)]palladium dichloride (PdCl2 · dppf) shows the highest catalitic activity in this reaction. A series of new mono- and diaryl [2.2]paracyclophane derivatives with various substituents in the arene ring have been synthesized using this catalyst. It was shown that it is possible to cross-couple organozinc [2.2]paracyclophane derivatives with aromatic bromides. The composition and structure of the compounds obtained have been established on the basis of elemental analysis and spectral data. Some correlations between the structure and spectral parameters of mono- and diarylsubstituted [2.2]paracyclophanes have been found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1081–1085, June, 1994.The present work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5246).The authors wish to express their gratitude to Prof. N. A. Bumagin for his scientific interest and helpful discussions. 相似文献
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The synthesis of a variety of new 4,5-disubstituted [2.2]paracyclophane derivatives has been achieved employing different cross-coupling reactions. By this methodology, a heteroatom-variation of successful catalyst ligands was achieved, giving rise to a modular ligand system. The X-ray structure of 4-hydroxy-5-(1′-hydroxy-1′-phenylethyl)-[2.2]paracyclophane was determined to elucidate the configuration. Additionally, a diastereoselective synthesis of planar- and central-chiral 4-([2.2]paracyclophanyl)ethylamine was achieved, thus resulting in a planar- and central-chiral phenyl ethylamine analogue. 相似文献
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Takaya Kimoto Dr. Nobuo Tajima Prof. Dr. Michiya Fujiki Dr. Yoshitane Imai 《化学:亚洲杂志》2012,7(12):2836-2841
The solution‐dispersed‐state and polymer‐dispersed‐state circular dichroism (CD) and circularly polarized luminescence (CPL) properties of chiral binaphthyl fluorophores could be controlled by the choice of open‐ or closed‐type substituents on the binaphthyl units and by the axial chirality of the binaphthyls. 相似文献
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D. Yu. Antonov E. V. Sergeeva E. V. Vorontsov V. I. Rozenberg 《Russian Chemical Bulletin》1997,46(11):1897-1900
An efficient three-step synthesis of [2.2]paracyclophane-pseudo-ortho-dicarboxylic acid by dibromination of [2.2]paracyclophane, thermal isomerization of the resultingpseudopara-dibromide topseudo-ortho-isomer, followed by lithiation/carboxylation was developed. The possibility of preparation of two other novelpseudo-ortho-disubstituted carbonyl derivatives, 4-carboxy-12-(1-oxopenthyl)-[2.2]paracyclophane and di(4-carboxy[2.2]paracyclophanyl-12)ketone,
was demonstrated when an excess of lithiation reagent (4 or 10 eq.) was used in the final step.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2001–2004, November, 1997. 相似文献
16.
Planar chiral hydroxy derivatives of [2.2]paracyclophane as auxiliaries for asymmetric allylboration
N. V. Vorontsova R. P. Zhuravsky E. V. Sergeeva E. V. Vorontsov Z. A. Starikova V. I. Rozenberg 《Russian Chemical Bulletin》2007,56(11):2225-2231
Allylboronic esters with various structures were synthesized for the first time based on [2.2]paracyclophane derivatives containing
one or two hydroxy groups. It was demonstrated that these esters can be used as chiral inductors in the asymmetric allylboration
of benzaldehyde. The highest enantiomeric excess of 1-phenylbut-3-en-1-ol (60%) was achieved in the reactions with acyclic
bis-O,O′-(paracyclophanyl) allylboronates based on (S)-4-hydroxy-and (S)-12-bromo-4-hydroxy[2.2]paracyclophanes. (S)-4-Hydroxy[2.2]paracyclophane was studied by X-ray diffraction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2149–2155, November, 2007. 相似文献
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K. P. Butin A. A. Moiseeva T. V. Magdesieva E. V. Sergeeva V. I. Rozenberg V. G. Kharitonov 《Russian Chemical Bulletin》1994,43(5):783-789
The potentials of electrochemical oxidation (
) and reduction (
) of monobromo- and isomeric di- and tribromo[2.2]paracyclophanes as well as
of mono-, di-, and tribromobenzenes were measured in acetonitrile. The similarity between the properties ofpseudo-para-disubstituted cyclophanes andmeta-disubstituted benzenes, on the one hand, andpseudo-meta-disubstituted cyclophanes andpara-disubstituted benzenes, on the other hand, was confirmed by the existence of a linear relationship between
of bromo-substituted [2.2]paracyclophanes and
of the corresponding bromo-substituted benzenes. The results were explained in terms of the qualitative theory of molecular orbitals, taking into account a through space interaction between the -systems of the benzene rings.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 839–845, May, 1994.The authors wish to express their gratitude to Professor R. Hoffmann (Cornell University, USA) for a useful discussion and criticisms of the text of this paper.This work was financially supported by the Russian Foundation for Basic Research (Project 93-03-5246). 相似文献
18.
Masayuki Gon Prof. Dr. Yasuhiro Morisaki Risa Sawada Prof. Dr. Yoshiki Chujo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(7):2291-2298
Optically active, Fréchet‐type dendrimers containing an emissive X‐shaped π‐electron system as the core unit were synthesized. Gram‐scale optical resolution and transformations of 4,7,12,15‐tetrasubstituted [2.2]paracyclophanes were also carried out. The high‐generation dendrons effectively absorbed UV light and transferred energy to the core, resulting in high photoluminescence (PL) from the core. In addition, the dendrons sufficiently isolated the emissive X‐shaped conjugated core and bright emission was observed from both thin films and solutions. Intense circularly polarized luminescence (CPL) was observed from the thin film. The dendrimer films exhibited excellent optical properties, such as large molar extinction coefficients, high fluorescence quantum efficiencies, intense PL and CPL, and large CPL dissymmetry factors. 相似文献
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Takahito Itoh Siro Okuoka Masataka Kubo Shouji Iwatsuki 《Journal of polymer science. Part A, Polymer chemistry》1995,33(3):359-363
1,1,9,9-Tetrafluoro[2.2]paracyclophane ( 1 ) was prepared successfully as white crystals in 72% yield via two-step reactions from 1,9-diketo[2.2]-paracyclophane. The polymerization of 1 by the vapor deposition method was carried out at pyrolysis temperature range of 400 to 800°C and deposition temperature range of ?20 to 20°C, and a tough, transparent poly(α,α-difluoro-p-xylylene) film was obtained in 72% yield at the pyrolysis temperature of 750°C and the deposition temperature of ?20°C. It was found that the pyrolysis of 1 gave a reactive α,α-difluoro-p-xylylene, which polymerized on the head-to-tail addition to give poly(α,α-difluoro-p-xylylene). Some properties such as solubility, thermal stability, glass transition temperature, and density for poly(α,α-difluoro-p-xylylene) were studied. © 1995 John Wiley & Sons, Inc. 相似文献