Tripivaloylmethane [systematic name: 4-(2,2-dimethylpropanoyl)-2,2,6,6-tetramethylheptane-3,5-dione], C(16)H(28)O(3), is a 1,3,3'-triketone with C(3) molecular symmetry, prepared by alpha-acylation of 2,2,6,6-tetramethylheptane-3,5-dione with 2,2-dimethylpropanoyl anhydride in the presence of barium metal. The molecules are conformationally chiral and pack so that each molecular site is occupied with equal probability by the two enantiomers. The carbonyl groups of the two superimposed enantiomeric molecules are at an angle of 75.4 (16) degrees .
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http://dx.doi.org/10.1107/S0108270107012474 | DOI Listing |
Chiral amines and amino alcohols form an important category of molecules employed in the designing of new drugs and catalyst. Herein, we present a helically-twisted stereodynamic dialdehyde probe 1 for the determining of absolute configuration, and enantiomeric excess of chiral amine and amino alcohols. Probe 1 is based on the pyridine-2,6-dicarboxamide (PDC) core and undergoes rapid interconversion between the P- and M- conformers.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Clemens-Schöpf-Institute for Organic Chemistry and Biochemistry, Technical University of Darmstadt, Peter-Grünberg-Str.16, 64287, Darmstadt, Germany.
Modern nuclear magnetic resonance (NMR) methods like carbon relaxation dispersion in the rotating frame (C-R) and proton chemical exchange saturation transfer (H-CEST) are key methods to investigate molecular recognition in biomacromolecules and to detect molecular motions on the μs to s timescale, revealing transient conformational states. Changes in kinetics can be linked to binding, folding, or catalytic events. Here, we investigated whether these methods allow detection of changes in the dynamics of a small, highly selective peptide catalyst during recognition of its enantiomeric substrates.
View Article and Find Full Text PDFEur J Med Chem
January 2025
Beijing National Laboratory for Molecular Science (BNLMS), CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China; University of Chinese Academy of Sciences, Beijing, 100049, China. Electronic address:
Six C-6 fluorinated d-swainsonine derivatives and their enantiomers have been designed based on initial docking calculations, and synthesized from enantiomeric ribose-derived aldehydes, respectively. Glycosidase inhibition assay of these derivatives with d-swainsonine (1) and l-swainsonine (ent-1) as contrasts found that the C-6 fluorinated d-swainsonine derivatives with C-8 configurations as R (α) showed specific and potent inhibitions of jack bean α-mannosidase (model enzyme of Golgi α-mannosidase II); whereas their enantiomers with C-8 configurations as S (β) were powerful and selective α-l-rhamnosidase inhibitors. Molecular docking calculations found the C-6 fluorinatedd-swainsonine derivatives 21, 24 and 25 with highly coincident binding conformations with d-swainsonine (1) in their interactions with the active site of α-mannosidase (PDB ID: 1HWW).
View Article and Find Full Text PDFMethods Mol Biol
November 2024
Faculty of Chemistry, University of Gdańsk, Fahrenheit Union of Universities in Gdańsk, Gdańsk, Poland.
Coarse graining is usually considered as a tool to extend the time and size scale of simulations. However, leaving out the atomistic details to keep their fingerprints in a coarse-grained model also enables us to understand better structure formation and dynamics. In this chapter, by using our scale-consistent theory of coarse graining, we demonstrate that the coarse-grained terms corresponding to the coupling between local conformational states of amino-acid residues explain secondary-structure propagation along polypeptide backbone to stabilize -helices and -strands in proteins and direct the loops preceding and following such segments of protein structure.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry, The University of British Columbia, Vancouver, BC V6T 1Z1, Canada.
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