A novel ligand exchange approach to catalytic asymmetric deprotonation-electrophilic trapping has been developed that uses 1.3 equiv of s-BuLi, 0.06-0.2 equiv of chiral diamine ((-)-sparteine or a (+)-sparteine surrogate), and 1.2 equiv of achiral bispidine. The methodology is illustrated with a range of examples and gives access to either enantiomer of useful chiral products in good yields using substoichiometric amounts of chiral diamines.
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http://dx.doi.org/10.1021/ja056026d | DOI Listing |
Org Lett
January 2025
Institute of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan.
Multiple Diels-Alder reactions are a powerful method to construct large asymmetric scaffolds, but these reactions often produce numerous isomers. We now report a triple Diels-Alder reaction between a cyclic furan trimer and -substituted maleimides, achieving selective synthesis of a single asymmetric tris-adduct. The stereoselectivity of cycloaddition to π-extended furan derivatives was clarified by the experimental analysis of intermediates and theoretical calculations.
View Article and Find Full Text PDFEnzymatic asymmetric synthesis of l-phenylglycine by amino acid dehydrogenases has potential for industrial applications; however, this is hindered by their low catalytic efficiency toward high-concentration substrates. We identified and characterized a novel leucine dehydrogenase (LeuDH) with a high catalytic efficiency for benzoylformic acid via directed metagenomic approaches. Further, we obtained a triple-point mutant LeuDH-EER (D332E/G333E/L334R) with improved stability and catalytic efficiency through the rational design of distal loop 13.
View Article and Find Full Text PDFChem Soc Rev
January 2025
Pingyuan Laboratory, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453007, Henan, P. R. China.
The use of olefins in the construction of cyclic compounds represents a powerful strategy for advancing the pharmaceutical industry. Photocycloaddition has attracted significant interest from chemists due to its ability to exploit simple and readily available olefins along with their reaction patterns under mild conditions. Moreover, the sustainable and versatile pathways for generating highly reactive intermediates can greatly enrich both substrate diversity and reaction patterns.
View Article and Find Full Text PDFNano Lett
January 2025
Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Material Sciences and Chemical Engineering, Harbin Engineering University, Harbin 150001, P. R. China.
Dual atomic nanozymes (DAzymes) are promising for applications in the field of tumor catalytic therapy. Here, integrating with ultrasmall FeC nanoclusters, asymmetric coordination featuring Janus Zn-Fe dual-atom sites with an ON-Fe-Zn-N moiety embedded in a carbon vacancy-engineered hollow nanobox (Janus ZnFe DAs-FeC) was elaborately developed. Theoretical calculation revealed that the synergistic effects of Zn centers acting as both adsorption and active sites, oxygen-heteroatom doping, carbon vacancy, and FeC nanoclusters jointly downshifted the d-band center of Fe 3d orbitals, optimizing the desorption behaviors of intermediates *OH, thereby significantly promoting catalytic activity.
View Article and Find Full Text PDFRSC Chem Biol
January 2025
Department of Chemistry, Emory University Atlanta GA 30322 USA
Members of the old yellow enzyme (OYE) family utilize a flavin mononucleotide cofactor to catalyze the asymmetric reduction of activated alkenes. The 2-enoate reductase (2-ER) subfamily are of particular industrial relevance as they can reduce α/β alkenes near electron-withdrawing groups. While the broader OYE family is being extensively explored for biocatalytic applications, oxygen sensitivity and poor expression yields associated with the presence of an Fe/S cluster in 2-ERs have hampered their characterization.
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