The determination of the enantiomeric excess and absolute configuration of chiral compounds is indispensable in synthetic, pharmaceutical, and biological chemistry. In this article, we describe an efficient 19 F nuclear magnetic resonance (NMR)based analytical protocol for determining the enantiomeric excess and absolute configuration of in situ fluorine-labeled amines and alcohols. 2-Fluorobenzoylation was used to convert analytes to fluorinated amides or esters. The resulting F-labeled analytes were mixed with a cationic cobalt(III) complex, [Co]BArF, resulting in clean baseline peak separations of analyte enantiomers in 19 F{ 1 H} NMR spectra. The measured Δδ RS signs were unambiguously used to correlate the absolute configurations of amines, amino alcohols, and alcohols. Moreover, the structure-dependent 19 F{ 1 H} NMR signals enabled absolute configuration determination by analyzing the relative chemical shifts of enantiopure analyte samples with [Co]BArF and ent-[Co]BArF.
The Pd‐catalyzed γ‐position sp3−C−H arylation of primary amines bearing an aliphatic chain or cycloalkyl substituent and related mechanistic studies are disclosed. 3‐Bromo‐2‐hydroxybenzaldehyde plays a key role in γ‐position sp3−C−H arylation as a transient directing group (TDG) to assist the regio‐ and stereoselective C−H activation of a Pd catalyst, and the development of a tandem reaction to transform 1°‐amines into γ‐aryl‐substituted ketones demonstrates synthetic utility. Density functional theory (DFT)‐based calculations revealed the detailed reaction mechanism and the origins of the high selectivity (γ‐position and cis‐only). The X‐ray crystal structure of the isolated endo‐palladacycle intermediate supported the DFT results, and a kinetic isotope experiment confirmed the results of DFT calculations indicating that the C−H activation step via simultaneous palladation and deprotonation is rate‐determining.
We present a novel approach utilizing 19F-nuclear magnetic resonance (NMR) spectroscopy for serum amine profiling. Our method introduces a highly efficient and reliable technique for fluorine labeling of amine metabolites via Schiff base formation. By employing this fluorine labeling, we successfully achieve accurate identification and quantification of amine metabolites in human serums, providing valuable insights for metabolomics research.
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