cis,anti,cis-Tricyclo[7.4.0.0(2,8)]tridec-10-ene (13TCT) undergoes [1,3] sigmatropic rearrangements at 315 °C in the gas phase to the si product 1 and to the sr product 2 with si/sr = 2.1. The dominant thermal isomerization process, however, is epimerization at C8 to afford product 3. That stereomutation at C8 occurs 50% faster than the si and sr shifts combined.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jo300082a | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Mechanisms of the Photomechanical Response in Thin-Film Dye-Doped Glassy Polymers.
Polymers (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 PDFBenzo-Fused Phosphepines: Synthesis by Gold(I)-Catalyzed Intramolecular Hydroarylation and Ring Inversion.
Chemistry
January 2025
Osaka Metropolitan University: Osaka Koritsu Daigaku, Chemistry, 3-3-138 Sugimoto, Sumiyoshi-ku, 558-8585, Osaka, JAPAN.
Gold(I)-catalyzed intramolecular hydroarylation of dialkynyl(biaryl)phosphine oxides provided versatile benzo-fused phosphepine oxides. O-exo adducts were obtained as the major product, and O-endo adducts were the minor product. O-exo and O-endo indicate the position of an oxygen atom with respect to the central phosphepine framework.
View Article and Find Full Text PDFColumnar Mesophases and Organogels Formed by H-Bound Dimers Based on 3,6-Terminally Difunctionalized Triphenylenes.
Gels
December 2024
Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires C1428EGA, Argentina.
A series of triphenylene (TP) compounds-denoted 3,6-THTP-DiCOH-bearing four hexyloxy ancillary chains and two variable-length alkoxy chains terminally functionalized with hydroxyl groups have been synthesized and characterized. The shorter homologs revealed mesogenic characteristics, giving rise to thermotropic mesophases in which π-stacked columns of H-bound dimers self-organize yielding superstructures. Molecular-scale models are proposed to account for their structural features.
View Article and Find Full Text PDFComputational Study on the Dynamics of a Bis(benzoxazole)-Based Overcrowded Alkene.
J Phys Chem A
January 2025
Department of Chemistry - Ångström Laboratory, Uppsala University, Box 523, Uppsala 751 20, Sweden.
Understanding and controlling molecular motions is of pivotal importance for designing molecular machinery and functional molecular systems, capable of performing complex tasks. Herein, we report a comprehensive theoretical study to elucidate the dynamic behavior of a bis(benzoxazole)-based overcrowded alkene displaying several coupled and uncoupled molecular motions. The benzoxazole moieties give rise to 4 different stable conformers that interconvert through single-bond rotations.
View Article and Find Full Text PDFHydrogen-Bonding-Driven Design of Organic-Inorganic Hybrid Ferroelastics with Reversible Photoisomerization.
Inorg Chem
January 2025
Department of Chemistry & CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal.
The development of photoresponsive ferroelastics, which couple light-induced macroscopic mechanical and microscopic domain properties, represents a frontier in materials science with profound implications for advanced functional applications. In this study, we report the rational design and synthesis of two new organic-inorganic hybrid ferroelastic crystals, (MA)(MeN)[Fe(CN)(NO)] (MA = methylammonium) () and (MA)(MeNOH)[Fe(CN)(NO)] (), using a dual-organic molecular design strategy that exploits hydrogen-bonding interactions for tailoring ferroelastic properties. Specifically, exhibits a two-step phase transition at 138 and 242 K, while the introduction of a hydroxyl group in stabilizes its ferroelastic phase to a significantly higher temperature, achieving a phase transition at 328 K, 86 K above that of .
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!