Article
Chemistry, Multidisciplinary
Luke Hodson, Kevin J. Visagie, Michael-Phillip Smith, Leigh Loots, David Kuter, Tregen M. Snayer, Gareth E. Arnott
Summary: Inherently chiral calix[4]arenes with C-4-symmetry are rare and difficult to synthesise, but this study successfully obtained a high-yield product through a specific reaction. The use of a specific chiral group enabled the separation of the diastereomers formed, leading to the pure enantiomers.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Oleksandr A. Yesypenko, Anastasia O. Osipova, Oleksandr O. Tribrat, Sergii O. Kravchenko, Oleg M. Usachov, Viktoriya V. Dyakonenko, Aleksey B. Ryabitskii, Vladimir V. Pirozhenko, Svitlana Shishkina, Alexander B. Rozhenko, Vitaly Kalchenko
Summary: In this study, all three possible inherently chiral (cS)-propyloxy-octyloxy-calix[4]arene acetic acids were synthesized and their absolute configuration was determined. The complexation of these acetic acids with various chiral compounds was investigated using molecular modeling and H-1 NMR spectroscopy, revealing enantioselectivity in the binding of R- and S-forms of 2-aminobutanol.
Article
Chemistry, Organic
Oleksandr O. Trybrat, Oleksandr A. Yesypenko, Svitlana Shishkina, Eduard B. Rusanov, Yevgen A. Karpichev, Vitaly Kalchenko
Summary: This paper demonstrates a new method for synthesizing inherently chiral calix[4]arenes, using 25-propyloxy-26,27-dibenzoyloxy-calix[4]arene as a precursor and developing sequential regioselective debenzoylation and electrophilic substitution methods. Inherently chiral calix[4]arenes with different functional groups on the upper rim were successfully synthesized.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yu-Zhen Zhang, Meng-Meng Xu, Xu-Ge Si, Jun-Li Hou, Quan Cai
Summary: An efficient approach for the enantioselective synthesis of inherently chiral calix[4]arenes via palladium-catalyzed asymmetric intramolecular C-H arylations is reported. The use of a chiral bifunctional phosphine-carboxylate ligand successfully induced inherent chirality on macrocyclic scaffolds, resulting in a wide range of calix[4]arenes with fluorenone motifs obtained with good yields and excellent enantioselectivities. Diverse transformations of the products demonstrate the synthetic utility of this method, substantially expanding the chemical space of chiral calix[4]arenes. Investigations of photophysical and chiroptical properties reveal the great potential of inherent chirality in the development of organic optoelectronic materials for calix[4]arenes bearing two fluorenone moieties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Xu Ying, Zhenhua Zhu, Xiao-Lei Li, Jinkui Tang
Summary: We report two pairs of enantiomers of Co(II)and Zn(II)-based metallacycles constructed by coordination-driven self-assembly between homochiral 1,1 '-bi-2-naphthol-derived ligands featuring two kinds of coordination pockets and transition metal ions. Remarkably, they exhibit calix[4]arene-like topological structures and fascinating chiral cavities, having potential in enantioselective recognition.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Physical
Minami Odagi, Kazuo Nagasawa
Summary: This paper describes recent progress in chiral hypoiodite-catalyzed enantioselective oxidative bond-forming reactions, focusing on the applications of ammonium and guanidinium salts as onium iodites in carbon-oxygen, carbon-nitrogen, and carbon-carbon bond formation reactions.
Article
Chemistry, Physical
Jae Ho Shim, Ji Yeon Lee, Hyeon Soo Kim, Deok-Chan Ha
Summary: The study developed a catalyst with N-selectivity for the nitroso aldol reaction, using a quantum calculation. The reaction mechanism was determined and optimized, resulting in a high yield of the product with high enantioselectivity. The catalyst provides a less expensive and more environmentally friendly alternative for the reaction.
Article
Chemistry, Inorganic & Nuclear
Stanislav Bezzubov, Kirill Ermolov, Alexander Gorbunov, Paulina Kalle, Ivan Lentin, Gennadij Latyshev, Vladimir Kovalev, Ivan Vatsouro
Summary: Conventional cyclometalation of calix[4]arene bis(aryltriazoles) with iridium(iii) chloride hydrate results in unique meso architectures, where the dinuclear complexes contain independent or coupled iridium pairs which can be further modified by replacing chloride bridges with ancillary ligands.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Organic
Qi Yin, Xiaolu Wen, Yiwei Chen, Xiangnan Gong, Lin Hu
Summary: The efficient catalytic asymmetric [4 + 1] reaction developed in this study enables the synthesis of functionalized organic compounds with consecutive quaternary and tertiary carbon stereocenters in high diastereoselectivities and enantioselectivities. The products obtained can be readily transformed into chiral compounds through debenzoylation and alkylation reactions, providing a versatile platform for further chemical transformations.
Article
Chemistry, Medicinal
Zoya I. Kazantseva, Igor A. Koshets, Oleksandr O. Trybrat, Oleksandr A. Yesypenko, Vitali I. Kalchenko
Summary: The study investigated the enantiodiscrimination properties of stereomerically pure inherently chiral calix[4]arene acetic acids and their derivatives in liquid and gaseous phases with respect to 1-phenylethylamine stereoisomers using H-1 NMR and QCM techniques. It was found that sensors based on calix[4]arene acetic acids are capable of recognizing R- and S-forms of 1-phenylethylamine in the gaseous phase within a concentration range of 10-400 ppm.
Article
Chemistry, Inorganic & Nuclear
Mamina Bhol, Guilhem Claude, Maximilian Roca Jungfer, Ulrich Abram, Malaichamy Sathiyendiran
Summary: In this study, calix[4]arene-analogous technetium supramolecules and rhenium-based macrocycles were successfully assembled by using specific ligands and starting materials. The structures of these molecules were characterized in detail.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Yujiro Hayashi, Masashi Tomikawa, Naoki Mori
Summary: The asymmetric cross-aldol reaction is a synthetically relevant reaction. The reactivity and stereoselectivity of different catalysts were compared for the reaction, and it was found that the proper selection of catalysts can lead to the synthesis of chiral building blocks with high diastereoselectivities and enantioselectivities.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Eri Ogino, Satoru Kuwano, Takayoshi Arai
Summary: In this study, chiral catalyst AMB2 was used to successfully catalyze the asymmetric epoxidation of acrylonitriles, resulting in highly enantioselective chiral epoxides.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Kazutaka Shibatomi
Summary: This paper summarizes our recent efforts in the enantioselective organocatalytic synthesis of chiral halogenated compounds. The discussion includes enantioselective alpha-halogenation of aldehydes, decarboxylative chlorination of beta-keto acids, and enantioselective C-C bond formation at the trifluoromethylated prochiral carbon to yield organohalides with chlorinated, fluorinated, or trifluoromethylated chiral stereogenic centers. Common organocatalysts such as Jorgensen-Hayashi catalyst and cinchona alkaloid-derivatived catalyst were applied, and novel chiral amine catalysts were developed for these reactions. Stereospecific derivatizations of the chiral halogenated compounds via nucleophilic substitution are also discussed, resulting in the synthesis of many novel chiral compounds that have not been reported before, even as racemates.
Article
Chemistry, Organic
Raghunath Chowdhury, Akhil K. Dubey, Sunil K. Ghosh
Summary: In this study, a Michael addition reaction of pyrazolin-5-ones with beta-silylmethylene malonates was successfully achieved using a squaramide catalyst derived from quinidine under mild reaction conditions. High yields and good to excellent enantioselectivities were obtained for chiral organosilanes appendage with pyrazole moiety. Furthermore, the scale-up reaction confirmed the practical reliability of this protocol.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.