Enantiospecific state transfer of chiral molecules is extremely important because enantiomers coexist in many biologically active compounds and play significantly different physiological, pharmacological, and biological roles. The inherently strong electric-dipole optical approaches based on the cyclic three-level model of chiral molecules have been extensively discussed. But, for the cases of large chiral molecules and/or chiral molecules of low asymmetry, the four-level model with two sub-loops is more realistic to describe the molecules. Based on the four-level model, we propose a pump-control approach to realize the highly efficient enantiospecific state transfer. In our approach, two pump pulses are applied to generate molecular coherence between the ground state and the first excited state of our working model. According to the coherence of the molecules, we adjust the phase and pulse area of the control pulse, then we obtain the highly efficient enantiospecific state transfer in the first excited working state. In addition, we further optimize the fraction of enantiopure samples by adjusting the area of the two pump pulses.
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http://dx.doi.org/10.1364/OE.528182 | DOI Listing |
J Am Chem Soc
January 2025
Department of Applied Chemistry, Anhui Province Engineering Laboratory for Green Pesticide Development and Application, and Anhui Province Key Laboratory of Crop Integrated Pest Management, Anhui Agricultural University, Hefei 230036, China.
Asymmetric catalysis involving a sulfoxide electrophile intermediate presents an efficient methodology for accessing stereogenic-at-sulfur compounds, such as sulfinate esters, sulfinamides, , which have garnered increasing attention in modern pharmaceutical sciences. However, as the aza-analog of sulfoxide electrophiles, the asymmetric issues about electrophilic sulfinimidoyl species remain largely unexplored and represent a significant challenge in sulfur stereochemistry. Herein, we exhibit an anionic stereogenic-at-cobalt(III) complex-catalyzed asymmetric synthesis of chiral sulfinamides via chiral sulfinimidoyl iodide intermediates.
View Article and Find Full Text PDFScience
December 2024
Department of Chemistry, Scripps Research, 10550 North Torrey Pines Road, La Jolla, CA, USA.
Modern medicinal chemists are targeting more complex molecules to address challenging biological targets, which leads to synthesizing structures with higher sp character (Fsp) to enhance specificity as well as physiochemical properties. Although traditional flat, high-fraction sp molecules, such as pyridine, can be decorated through electrophilic aromatic substitution and palladium (Pd)-based cross-couplings, general strategies to derivatize three-dimensional (3D) saturated molecules are far less developed. In this work, we present an approach for the rapid, modular, enantiospecific, and diastereoselective functionalization of piperidine (saturated analog of pyridine), combining robust biocatalytic carbon-hydrogen oxidation with radical cross-coupling.
View Article and Find Full Text PDFPhytochemistry
April 2025
Department of Crop and Soil Science, North Carolina State University, Raleigh, NC, USA. Electronic address:
Plant species can accumulate secondary metabolites in optically pure form or, occasionally, as enantiomeric mixtures. Interestingly, enantiomers of the same molecule can confer different biological activities. In tobacco (Nicotiana tabacum L.
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 PDFChem Sci
November 2024
Shenzhen Grubbs Institute, Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology 1088 Xueyuan Avenue Shenzhen P. R. China
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