The complex [MnCl(OPPh)] () is a bench-stable and easily prepared source of MnCl. It is prepared by treating acetonitrile solvated MnCl () with PhPO and collecting the resulting blue precipitate. is useful in coordination reactions by virtue of the labile PhPO ligands, and this is demonstrated through the synthesis of {Tpm*}MnCl (). In addition, methodologies in synthesis that rely on difficult or cumbersome to prepare solutions of reactive MnCl can be accomplished using instead. This is demonstrated through alkene dichlorinations in a wide range of solvents, open to air, and with good substrate scope. Light-accelerated halogenation and radical sensitive experiments support a radical mechanism involving stepwise Cl-atom transfer(s) from .
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http://dx.doi.org/10.1021/jacs.2c08509 | DOI Listing |
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11648269 | PMC |
Adv Sci (Weinh)
December 2024
Shanghai Frontiers Science Center of Drug Target Identification and Delivery, School of Pharmaceutical Sciences, Shanghai Jiao Tong University, Shanghai, 200240, China.
Given the widespread presence of fluoroalkyl functionalities in bioactive molecules, the development of fluoroalkylation reactions with bench-stable and easy-to-use fluoroalkylating reagents is highly desirable. In addition, realization of mono-, di-, tri-, or polyfluoroalkyation usually requires distinct types of fluoroalkylating reagents under different or even harsh reaction conditions, and a universal method to accomplish different hydrofluoroalkylation of alkenes is lacking. Herein, the use of quaternary fluoroalkyl alcohols is reported as the universal fluoroalkylating reagents to readily facilitate mono-, di-, tri-, or polyfluoroalkylation of a wide range of alkene substrates in high yields.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, P. R. China.
Reported herein is a convenient and efficient method for one-pot, catalytic reductive amination, as well as the first multi-component tandem reductive amination-functionalization of bench-stable and readily available common carboxylic esters. This method is based on the cationic [Ir(COD)]BArF-catalyzed chemoselective hydrosilylation of esters, followed by one-pot acid-mediated amination and nucleophilic addition. The reaction was conducted under mild conditions at a very low catalyst loading (0.
View Article and Find Full Text PDFOrg Lett
December 2024
Department of Organic Chemistry, Indian Institute of Science, Bangalore-560012, India.
A general and practical route to the synthesis of β-keto amino acid derivatives from aldehydes and bench stable imine surrogates is presented. Following the interrupted Polonovski strategy, the imine formed in situ was trapped by the catalytically generated Breslow intermediate in an aza benzoin reaction. The present strategy has been extended to the formal synthesis of florfenicol and an intermediate en route to vancomycin.
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.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany.
A VAPOL-derived phosphoramidite ligand is uniquely effective at reverting the regiochemical course of nickel-catalyzed reactions of aldehydes with carbamate-protected 5-amino-2,4-pentadienoates as "push/pull" dienes; the ensuing carbonyl α-amino-homoallylation reaction affords -configured -aminoalcohol derivatives in good yields with high optical purity. The reductive coupling is conveniently performed with a bench-stable Ni(0) precatalyst and EtB as the promoter.
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