The stereochemistries of geometric isomers of 4-(2-bromo-1,2-diphenylvinyl)phenol, 4-(2-bromo-1,2-diphenylvinyl)anisole, and 2-[p-(2-bromo-1,2-diphenylvinyl)phenoxy]triethylamine were determined by conversion of the phenolic analog to the ethers and subsequent comparison of physical properties with those of 2-[p-(2-chloro-1,2-diphenylvinyl)phenoxy]triethylamine of known stereochemistry.
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http://dx.doi.org/10.1002/jps.2600651036 | DOI Listing |
Org Lett
March 2025
Kekulé-Institute for Organic Chemistry and Biochemistry, University of Bonn, D-53121 Bonn, Germany.
The central hexaene core of the labile polyene antibiotic bacillaene bearing three -configured olefins was prepared with excellent geometrical purity by an iterative cross-coupling strategy, involving improved syntheses of bimetallic reagents and efficient protocols for stereoselective polyene generation, revealing insights into the origin of bacillaene's instability. Furthermore, a useful method for monitoring polyene iteration by UV-vis shift analyses and the absolute stereochemistry of this core by biosynthetic gene cluster analysis are reported.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Geometrically defined allylic alcohols with SE, SZ, RE and RZ stereoisomers serve as valuable intermediates in synthetic chemistry, attributed to the stereoselective transformations enabled by the alkenyl and hydroxyl functionalities. When an ideal scenario presents itself with four distinct stereoisomers as potential products, the simultaneous control vicinal stereochemistry in a single step would offer a direct pathway to any desired stereoisomer. Here, we unveil a metallaphotoredox migration strategy to access stereodefined allylic alcohols through vinylic C-H activation with aldehydes.
View Article and Find Full Text PDFJ Am Chem Soc
March 2024
School of Chemistry, University of Southampton, University Road, Southampton SO17 1BJ, U.K.
Mechanical stereochemistry arises when the interlocking of stereochemically trivial covalent subcomponents results in a stereochemically complex object. Although this general concept was identified in 1961, the stereochemical description of these molecules is still under development to the extent that new forms of mechanical stereochemistry are still being identified. Here, we present a simple analysis of rotaxane and catenane stereochemistry that allowed us to identify the final missing simple mechanical stereogenic unit, an overlooked form of rotaxane geometric isomerism, and demonstrate its stereoselective synthesis.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
March 2024
School of Electrical and Computer Engineering, Georgia Institute of Technology, Atlanta, GA 30332.
Chirality is a geometric property describing the lack of mirror symmetry. This unique feature enables photonic spin-selectivity in light-matter interaction, which is of great significance in stereochemistry, drug development, quantum optics, and optical polarization control. The versatile control of optical geometry renders optical metamaterials as an effective platform for engineered chiral properties at prescribed spectral regimes.
View Article and Find Full Text PDFChem Sci
February 2024
Department of Statistics 24-29 St Giles' Oxford OX1 3LB UK
The last few years have seen the development of numerous deep learning-based protein-ligand docking methods. They offer huge promise in terms of speed and accuracy. However, despite claims of state-of-the-art performance in terms of crystallographic root-mean-square deviation (RMSD), upon closer inspection, it has become apparent that they often produce physically implausible molecular structures.
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