A degree of chirality is a function that purports to measure the amount of chirality of an object: it is equal for enantiomers, vanishes only for achiral or degenerate objects and is similarity invariant, dimensionless and normalisable to the interval [0,1]. For a tetrahedron of non-zero three-dimensional volume, achirality is synonymous with the presence of a mirror plane containing one edge and bisecting its opposite, and hence it is easy to design degree-of-chirality functions based on edge length that incorporate all constraints. It is shown that such functions can have largest maxima at widely different points in the tetrahedral shape space, and by incorporation of appropriate factors, the maxima can be pushed to any point in the space. Thus the phrase "most chiral tetrahedron" has no general meaning: any chiral tetrahedron is the most chiral for some legitimate choice of degree of chirality.
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http://dx.doi.org/10.1002/chem.200400869 | DOI Listing |
Science
January 2025
Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore.
Axions, hypothetical elementary particles that remain undetectable in nature, can arise as quasiparticles in three-dimensional crystals known as axion insulators. Previous implementations of axion insulators have largely been limited to two-dimensional systems, leaving their topological properties in three dimensions unexplored in experiment. Here, we realize an axion insulator in a three-dimensional photonic crystal and probe its topological properties.
View Article and Find Full Text PDFAstrobiology
December 2024
Dipartimento di Chimica, Università degli Studi di Bari Aldo Moro, Bari, Italy.
Agent-based simulations are set to describe the early biotic selection of oligomers made of monomers of different chirality. The simulations consider the spatial distribution of agents and resources, the balance of biomass of different chirality, and the balance of chemical energy. Following the well-known Wald's hypothesis, a disadvantage is attributed to the change in chirality along the biochemical sequence.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Max-Planck-Institut fur Kohlenforschung, Organometallic Chemistry, Kaiser-Wilhelm-Platz 1, 45470, Mülheim/Ruhr, GERMANY.
Ynamides, when reacted with H2 or HBpin in the presence of [Cp*RuCl]4, convert into chiral-at-metal Fischer carbenes by regioselective gem-hydrogenation or gem-hydroboration of the polarized triple bond, respectively. gem-Hydroboration concomitantly affords a carbogenic borylated stereocenter adjacent to the ruthenium carbene unit, the configuration of which can be controlled using an Evans auxiliary. These are the first examples of asymmetric gem-addition reactions to alkynes known in the literature; representative pianostool ruthenium carbene complexes formed by this unconventional route were characterized by crystallographic and spectroscopic means.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, United States.
A Brønsted acid-catalyzed enantioselective synthesis of ()-1,3-butadienyl-2-carbinols is developed. By employing a chiral phosphoric acid as the catalyst, a variety of 1,3-butadienyl-2-carbinols were obtained in good yields with excellent -selectivities and enantiopurities from α-alkyl-substituted homoallenyl boronates.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Changchun Institute of Applied Chemistry Chinese Academy of Sciences: Chang Chun Institute of Applied Chemistry Chinese Academy of Sciences, Jilin Province Key Lab of Green Chemistry and Process, CHINA.
A modular approach was developed for the first catalytic asymmetric total syntheses of naturally occurring C30 terpene quinone methides and their non-natural stereoisomers, which feature the presence of an unprecedented spiro[4.4]nonane-containing 6-6-6-5-5-3 hexacyclic skeleton. Resting on a chiral phosphinamide-catalyzed enantioselective reduction of 2,2-disubstituted cyclohexane-1,3-dione, a concise route for the synthesis of enantioenriched 6-6 bicyclic fragment was developed.
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