Controlling dynamic chirality and memorizing the controlled chirality are important. Chirality memory has mainly been achieved using noncovalent interactions. However, in many cases, the memorized chirality arising from noncovalent interactions is erased by changing the conditions such as the solvent and temperature. In this study, the dynamic planar chirality of pillar[5]arenes was successfully converted into static planar chirality by introducing bulky groups through covalent bonds. Before introducing the bulky groups, pillar[5]arene with stereogenic carbon atoms at both rims existed as a pair of diastereomers, and thus showed planar chiral inversion that was dependent on the chain length of the guest solvent. The pS and pR forms, regulated by guest solvents, were both diastereomerically memorized by introducing bulky groups. Furthermore, the diastereomeric excess was amplified by crystallization of the pillar[5]arene. The subsequent introduction of bulky groups yielded pillar[5]arene with an excellent diastereomeric excess (95 % de).
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1002/anie.202217971 | DOI Listing |
Adv Mater
January 2025
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.
Direct understanding of the formation and crystallization of low-dimensional (LD) perovskites with varying dimensionalities employing the same bulky cations can offer insights into LD perovskites and their heterostructures with 3D perovskites. In this study, the secondary amine cation of N-methyl-1-(naphthalen-1-yl)methylammonium (M-NMA) and the formation dynamics of its corresponding LD perovskite are investigated. The intermolecular π-π stacking of M-NMA and their connection with inorganic PbI octahedrons within the product structures control the formation of LD perovskite.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
New Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
The asymmetric Tsuji-Trost reaction has been extensively studied due to its importance in establishing stereogenic centers, often adjacent to an -olefin moiety in organic molecules. The generally preferential formation of chiral -olefin products is believed to result from the thermodynamically more stable -π-allylpalladium intermediate. The rapid associative π-σ-π isomerization makes it challenging to synthesize chiral -olefin products via the transient -π-allylpalladium intermediate.
View Article and Find Full Text PDFSci Rep
January 2025
Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznańskiego 8, Poznan, 61 614, Poland.
The embellishing of the macrocycle core with sulfur substituents of varied sterical requirements changes the structural dynamics of chiral, triangular polyimines. Despite their formal high symmetry, these compounds adopt diverse conformations, in which the macrocycle core represents a non-changeable unit. DFT calculations reveal that the mutual arrangement of sulfur-containing substituents is controlled mainly by sterical interactions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Oak Ridge National Laboratory, Chemical Sciences Division, UNITED STATES OF AMERICA.
Precise sub-Ångstrom-level porosity engineering, which is appealing in gas separations, has been demonstrated in solid carbon, polymer, and framework materials but rarely achieved in the liquid phase. In this work, a gas molecular sieving effect in the liquid phase at sub-5 Ångstrom scale is created via sophisticated porosity tuning in calixarene-derived porous liquids (PLs). Type II PLs are constructed via supramolecular complexation between the sodium salts of calixarene derivatives and crown ether solvents.
View Article and Find Full Text PDFInt Cancer Conf J
January 2025
Department of Hematology and Medical Oncology, Kanagawa Cancer Center, 2-3-2, Nakao, Asahi, Yokohama, Kanagawa 2418515 Japan.
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!