A Cu/CPA co-catalytic system has been developed for achieving the direct hydrophosphinylation of alkynes with phosphine oxides in delivering novel axially chiral phosphorus-containing alkenes in high yields and excellent enantioselectivities (up to 99 % yield and 99 % ee). DFT calculations were performed to elucidate the reaction pathway and the origin of enantiocontrol. This streamlined and modular methodology establishes a new platform for the design and application of new axially chiral styrene-phosphine ligands.
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http://dx.doi.org/10.1002/anie.202215820 | DOI Listing |
Sci Total Environ
January 2025
US Department of Agriculture, Agriculture Research Service, Hydrology and Remote Sensing Laboratory, Beltsville, MD, United States of America.
Metolachlor is the most heavily used member of acetanilide herbicides, which are noted for forming highly soluble metabolites in root zone soils soon after field application. The two primary metabolites of metolachlor, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOXA), retain the same chiral chemistry as their source and are important tracers of nitrate loading from agricultural cropland. New analytical methods for separating the isomers of MESA and MOXA, enable studies assessing changes in the abundance of atropisomer pairs of the carbon chiral enantiomers in environmental samples.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States.
Precisely controlling quantum states is relevant in next-generation quantum computing, encryption, and sensing. Chiral organic chromophores host unique light-matter interactions, which allow them to manipulate the quantized circular polarization of photons. Axially chiral organic scaffolds, such as helicenes or twisted acenes, are powerful motifs in chiral light manipulation.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
Axially chiral -VQMs have been extensively investigated as key intermediates to approach miscellaneous chiral structures. By sharp contrast, their structural isomers -VQMs have not been previously documented. The major reason, which results in the significant delay, may ascribe to the inherent challenges in the enantioselective activation of alkynes in a remote manner.
View Article and Find Full Text PDFBeilstein J Org Chem
January 2025
Department of Organic Chemistry, Faculty of Natural Science, Comenius University Bratislava, Mlynská dolina, Ilkovičova 6, 842 15 Bratislava, Slovakia.
Axial chirality is present in a variety of naturally occurring compounds, and is becoming increasingly relevant also in medicine. Many axially chiral compounds are important as catalysts in asymmetric catalysis or have chiroptical properties. This review overviews recent progress in the synthesis of axially chiral compounds via asymmetric organocatalysis.
View Article and Find Full Text PDFChirality
January 2025
Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Narashino, Japan.
The synthesis, structure, and circularly polarized luminescence (CPL) properties of axially chiral boron difluoride complexes are described. A series of optically pure bis (boron difluoride) complexes were prepared in 5 steps from commercially available (S)- or (R)-BINOL as starting materials. The complexes were found to exhibit similar yellow photoluminescence in solution, regardless of the type of substituents on the nitrogen atoms.
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