In this tutorial review, we discuss how recycling and stability advantages alone are frequently not sufficient to justify the effort necessary to immobilize chiral complexes unless additional advantages are found. Nanostructured solids with well-controlled surfaces and pores may act as nanoreactors, hindering or even blocking some of the reaction channels, and hence modifying the stereochemical result of the reaction. The use of support effects to improve or change the enantioselectivity is emerging as an interesting field, whose understanding might allow, in the near future, the design of chiral ligands better adapted to this strategy.
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http://dx.doi.org/10.1039/b806643b | DOI Listing |
Chemistry
January 2025
Natinal Institute of Adavanced Industrial Science and Technology, Interdisciplinary Research Center for Catalytic Chemistry, Higashi 1-1-1, 305-8565, Tsukuba, JAPAN.
Unprecedented (2E,4E,6Z,8Z)-nona-2,4,6,8-tetraenoate derivatives highly substituted by aryl groups have been synthesized by the reaction of rhodium complexes having aryl-substituted hexa-1,3,5-trienyl ligands with acrylates. These compounds have potential axial chirality, and their enantiomers are isolable by the chiral HPLC technique. Although the racemization barrier of isolated enantiomers was not high, it was found that a cyclic dimer synthesized by head-to-tail transesterification of a modified analog has quite a stable axial chirality even at a high temperature.
View Article and Find Full Text PDFElectrophoresis
January 2025
Institute for Infectious Diseases, University of Bern, Bern, Switzerland.
Computer simulation was utilized to characterize the electrophoretic processes occurring during the enantioselective capillary electrophoresis-mass spectrometry (CE-MS) analysis of ketamine, norketamine, and hydroxynorketamine in a system with partial filling of the capillary with 19 mM (equals 5%) of highly sulfated γ-cyclodextrin (HS-γ-CD) and analyte detection on the cathodic side. Provided that the sample is applied without or with a small amount of the chiral selector, analytes become quickly focused and separated in the thereby formed HS-γ-CD gradient at the cathodic end of the sample compartment. This gradient broadens with time, remains stationary, and gradually reduces its span from the lower side due to diffusion such that analytes with high affinity to the anionic selector become released onto the other side of the focusing gradient where anionic migration and defocusing occur concomitantly.
View Article and Find Full Text PDFAnal Chim Acta
February 2025
Institute of Physical and Analytical Chemistry, School of Exact and Natural Sciences, Tbilisi State University, 0179, Tbilisi, Georgia. Electronic address:
Background: Isotopologues resulting from the labelling of molecules with deuterium have attracted interest due to the isotope effect observed in chemistry and biosciences. Isotope effect may also play out in noncovalent interactions and mechanisms leading to intermolecular recognition. In chromatography, differences in retention time between isotopologues, as well as between isotopomers have been observed resulting in two different elution sequences (isotope effects): the normal isotope effect when heavier isotopologues retain longer than lighter analogues, and the inverse isotope effect featuring the opposite elution order.
View Article and Find Full Text PDFMolecules
January 2025
Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland.
Building on our previous studies, which have demonstrated that homochiral propagating species-(*,*)-[MeGa(-OCH(Me)COR)]-were crucial for the heteroselectivity of [MeGa(-OCH(Me)COMe)] in the ring-opening polymerization (ROP) of racemic lactide (-LA), we have investigated the effect of alkyl groups on the structure and catalytic properties of dialkylgallium alkoxides in the ROP of -LA. Therefore, we have isolated and characterized the -[RGa(-OCH(Me)COMe] (R = Et (), Pr () and -[RGa(-OCH(Me)CHN] (R = Et (), Pr ()) complexes, to demonstrate the effect of alkyl groups on the chiral recognition induced the formation of the respective homochiaral species-(*,*)-[RGa(-OCH(Me)COMe)] and (*,*)-[RGa(-OCH(Me)CHN]. Moreover, we have investigated the structure of (,)-[RGa(-OCH(Me)COMe] (R = Et ((,)-, R = Pr ((,)-,) and their catalytic activity in the ROP of -LA.
View Article and Find Full Text PDFInorg Chem
January 2025
Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, Zhengzhou 450002, P. R. China.
Three two-dimensional (2D) chiral Ag(I) complexes with formulas [Ag(L)(5-nipa)] (), [Ag(L)(5-nipa)] (), and {[Ag(L)(5-hipa)]·2HO} () were prepared through the reactions of AgO with enantiopure -monodentate N-donors (L/L) and different dicarboxylic acids bearing A (acceptor)-π-- and D (donor)-π--type structural features, where / = (-)/(+)-2-(4'-pyridyl)-4,5-pinene-pyridine, 5-Hnipa = 5-nitroisophthalic acid, and 5-Hhipa = 5-hydroxyisophthalic acid. A study of their nonlinear optical responses reveals that chiral and enantiomeric pairs with the A-π--type dicarboxylic acid ligand simultaneously display second- and third-harmonic generation (SHG and THG) responses, while chiral containing the D-π--type dicarboxylic acid ligand only exhibits a very strong THG response. The THG intensity of is 451 × α-SiO, being about 27 and 24 times larger than those of and , respectively.
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