Spiro compounds have been considered key scaffolds for pharmaceutical applications. Although many synthetic methods exist for monospirocycles, fewer approaches are known for dispirocycles. Here, we report a highly -selective method for constructing a 5/6/5-dispirocyclic structure containing pyrrolidine and γ-lactam rings with various substituents from a series of -arylpropiolamides. The high -selectivity would result from isomerization under thermodynamic control. - and -diastereomers can be in equilibrium, favoring -adducts.
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http://dx.doi.org/10.1021/acs.joc.2c02225 | DOI Listing |
Chem Pharm Bull (Tokyo)
January 2025
Department of Life Science and Biotechnology, Faculty of Chemistry, Materials and Bioengineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680, Japan.
Density functional theory calculations on the cyclization of di-t-butyl 2-(2-aminophenyl)-2-methyl malonate (1) to t-butyl 3-methyloxindole-3-carboxylate (2) reveal that acetic acid-assisted protonation of the carbonyl oxygen atom reduces the activation Gibbs free energy significantly lower than methanol-assisted pathways. Experimental data confirm that reaction concentration plays a pivotal role in oxindole formation. Experimental results also indicate distinct reaction mechanisms at low and high concentrations.
View Article and Find Full Text PDFPolymers (Basel)
January 2025
Department of Physics, Washington State University, Pullman, WA 99163, USA.
This work aims to determine the mechanism of the photomechanical response of poly(Methyl methacrylate) polymer doped with the photo-isomerizable dye Disperse Red 1 using the non-isomerizable dye Disperse Orange 11 as a control to isolate photoisomerization. Samples are free-standing thin films with thickness that is small compared with the optical skin depth to assure uniform illumination and photomechanical response throughout their volume, which differentiates these studies from most others. Polarization-dependent measurements of the photomechanical stress response are used to deconvolute the contributions of angular hole burning, molecular reorientation and photothermal heating.
View Article and Find Full Text PDFPolymers (Basel)
January 2025
Department of Chemistry and Pharmacy, Interdisciplinary Center for Molecular Materials, Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen, Germany.
pH-responsive polyamidoamine (PAMAM) dendrimers are used as well-defined building blocks to design light-switchable nano-assemblies in solution. The complex interplay between the photoresponsive di-anionic azo dye Acid Yellow 38 (AY38) and the cationic PAMAM dendrimers of different generations is presented in this study. Electrostatic self-assembly involving secondary dipole-dipole interactions provides well-defined assemblies within a broad size range (10 nm-1 μm) with various shapes.
View Article and Find Full Text PDFMetab Eng
January 2025
Biochemistry, Molecular, Cellular, and Developmental Graduate Group, University of California, Davis, Davis, CA, 95616, USA; Department of Chemistry, University of California, Davis, Davis, CA, 95616, USA. Electronic address:
D-allose is a rare monosaccharide, found naturally in low abundances. Due to its low-calorie profile and similar taste to sucrose, D-allose has the potential to become an ideal sugar substitute. D-allose also displays unique properties and health benefits that can be applied to various fields, including food and medicine.
View Article and Find Full Text PDFNano Lett
January 2025
Zhejiang Engineering Research Center for Tissue Repair Materials and Wenzhou Key Laboratory of Biomaterials and Engineering and Wenzhou Key Laboratory of Biophysics, Wenzhou Institute, University of Chinese Academy of Sciences, Wenzhou 325001, China.
Saccharides and peptides with markedly disparate stereochemical features serve as pivotal chiral molecular partners in living systems. The importance of glycosylation in influencing glycopeptide self-assembly has been recognized. However, how different chiral combinations of saccharides and peptides influence the macroscopic hydrogel mechanics, fiber nanomechanics, asymmetric molecular packing, and thermodynamic changes during glycopeptide self-assembly remains unknown.
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