Chiral ruthenium(II)-salen complexes [RuII(salen)(PPh3)2] catalyse asymmetric aziridination of alkenes with up to 83% ees, asymmetric amidation of silyl enol ethers with up to 97% ees, and allylic amidation of cholesteryl acetates with good regioselectivity.
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http://dx.doi.org/10.1039/b109272c | DOI Listing |
Chemistry
January 2025
School of Chemistry, Xi'an Jiaotong University, Xi'an, 710049, P. R. China.
Due to the diverse chemical and physical properties of functional groups, mild and controllable ligation methods are often required to construct complex drugs and functional materials. To make diverse sets of products with tunable physicochemical properties, it is also useful to employ complimentary ligation methods that adopt the same starting materials. Here, we disclose the efficient and modular synthesis of amides or thioamides through the chemical ligation of acylsilanes with amines, simply by turning a light on or off.
View Article and Find Full Text PDFMolecules
December 2024
Grupo Química-Física Molecular y Modelamiento Computacional (QUIMOL), Escuela de Ciencias Químicas, Universidad Pedagógica y Tecnológica de Colombia, Sede Tunja, Avenida Central del Norte, Boyacá 150003, Colombia.
Silylation is a widely used derivatization technique for the gas chromatographic analysis of benzodiazepines, a class of psychoactive drugs commonly encountered in forensic and biological samples. This study investigated the optimal experimental conditions for the silylation of benzodiazepines using ,-bis(trimethylsilyl)trifluoroacetamide containing 1% trimethylchlorosilane (BSTFA + 1% TMCS), a widely employed silylating agent. Ten structurally different benzodiazepines, including variations within the classic 1,4-benzodiazepine core and triazolo ring derivatives, were selected to address the effect of structural diversity on silylation.
View Article and Find Full Text PDFChem Sci
January 2025
Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Key Laboratory of Research and Development for Natural Products, School of Pharmacy, Yunnan University Kunming 650500 P. R. China
Hydrogen atom transfer (HAT) processes provide an important strategy for selective C-H functionalization. Compared with the popularity of 1,5-HAT processes, however, net-1,2-HAT reactions have been reported less frequently. Herein, we report a unique visible-light-mediated net-1,2-HAT of amidyl radicals for the synthesis of β-amido ketone derivatives.
View Article and Find Full Text PDFOrg Lett
December 2024
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 311121, P. R. China.
Catalytic hydrosilylation of 1,1-disubstituted enamides is one of the most challenging and synthetically useful processes in organosilicon chemistry and asymmetric catalysis. Herein, we report a rhodium-catalyzed enantioselective hydrosilylation of α-arylenamides with substituted hydrosilanes with the aid of chiral P-ligand, including newly developed spirophosphite ligands, giving various chiral β-silylated amides in excellent yields with good to excellent enantioselectivities (98:2 er after recrystallization). In addition, chiral β-silylated amines can be obtained by further functionalization of the hydrosilylation product.
View Article and Find Full Text PDFNat Commun
November 2024
Bioland Laboratory, Guangzhou, China.
α-Functionalized Si-, Ge-, B-, Se-, and S-amide moieties are present in many medicinally active molecules, but their synthesis remains challenging. Here, we demonstrate a high-throughput synthesis using amide-sulfoxonium ylides as carbene precursors in a Si-H, Ge-H, B-H, Se-H, and S-H insertion reactions to target a wide range of α-silyl, α-geryl, α-boryl, α-selenyl, and α-sulfur (hetero)amides. The process is featured as simple operation, mild conditions, broad substrate scope, high functional group compatibility, and excellent chemoselectivity.
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