Background: The combination of metal-catalyzed reactions and enzyme catalysis has been an essential tool for synthesizing chiral pharmaceutical intermediates in the field of drug synthesis. Metal catalysis commonly enables the highly efficient synthesis of molecular scaffolds under harsh organic conditions, whereas enzymes usually catalyze reactions in mild aqueous medium to obtain high selectivity. Since the incompatibility between metal and enzyme catalysis, there are limitations on the compatibility of reaction conditions that must be overcome.
Findings: We report a chemoenzymatic cascade reaction involved Palladium (Pd) catalyzed Suzuki-Miyaura coupling and whole-cell catalyzed C = O asymmetric reduction for enantioselective synthesis of value-added chiral alcohol. The cell membrane serves as a natural barrier can protect intracellular enzymes from organic solvents.
Conclusions: With dual advantages of cascade catalysis and biocompatibility, our work provides a rational strategy to harvest chiral alcohols in high yield and excellent enantioselectivity, as a channel to establish chemoenzymatic catalysis.
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http://dx.doi.org/10.1186/s40643-022-00560-0 | DOI Listing |
J Am Chem Soc
January 2025
BioCIS, Faculté de Pharmacie, Université Paris-Saclay, CNRS, Orsay 91400, France.
The endoperoxide scaffold is found in numerous natural products and synthetic substances of pharmaceutical interest. The main challenge to their synthetic access remains the preparation of chiral compounds due to the weakness of the peroxide bond, which limits the scope of available or applicable methods. Here, we demonstrate how peroxycarbenium species can be trapped by silylated nucleophiles with high enantioselectivities and diastereoselectivities when applicable, using a chiral imidophosphorimidate (IDPi) as a catalyst.
View Article and Find Full Text PDFAnal Chim Acta
February 2025
Key Laboratory of Molecular Medicine and Biotherapy, School of Life Science, Beijing Institute of Technology, No. 5 Zhongguancun South Street, Beijing, 100081, China. Electronic address:
Background: The metal organic cages (MOCs) are an emerging type of porous material that has attracted considerable research interest due to their unique properties, including good stability and well-defined intrinsic cavities. The chiral MOCs with porous structures have broad application prospects in enantiomeric recognition and separation. However, there are almost no relevant reports on chiral MOCs as chiral stationary phases (CSPs) for enantioseparation by high-performance liquid chromatography (HPLC).
View Article and Find Full Text PDFJ Org Chem
January 2025
Institute of Chemistry, Technical University of Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany.
Chiral heterocyclic alcohols and amines are frequently used building blocks in the synthesis of fine chemicals and pharmaceuticals. Herein, we report a one-pot photoenzymatic synthesis route for -Boc-3-amino/hydroxy-pyrrolidine and -Boc-4-amino/hydroxy-azepane with up to 90% conversions and >99% enantiomeric excess. The transformation combines a photochemical oxyfunctionalization favored for distal C-H positions with a stereoselective enzymatic transamination or carbonyl reduction step.
View Article and Find Full Text PDFMolecules
December 2024
School of Chemistry, South China Normal University, Guangzhou Key Laboratory of Analytical Chemistry for Biomedicine, GDMPA Key Laboratory for Process Control and Quality Evaluation of Chiral Pharmaceuticals, Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, Guangzhou 510006, China.
Oxazoles are important five-membered heterocycles that contain both nitrogen and oxygen atoms. Due to their wide range of biological activities, many oxazoles demonstrate potential for extensive application in various fields, including medicinal chemistry. Trifluoromethyl carbinol, an important pharmacophore, contains both trifluoromethyl and hydroxyl groups and is common in molecules with important biological activities.
View Article and Find Full Text PDFInorg Chem
January 2025
School of Science and Technology, Nottingham Trent University, Nottingham, Clifton Lane NG11 8NS, U.K.
We report the synthesis of three radical-cation salts of BEDT-TTF from racemic tris(oxalato)ferrate by electrocrystallization in the presence of chiral molecules. In the presence of enantiopure l-(+)-tartaric acid, we observe spontaneous resolution of the labile tris(oxalato)ferrate anion to produce the chiral radical-cation salt α-(BEDT-TTF)[Δ-Fe(CO)].[l-(+)-tartaric acid] which contains only the Δ enantiomer of Fe(CO).
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