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http://dx.doi.org/10.1103/physrevc.46.455 | DOI Listing |
J Am Chem Soc
November 2024
Process Research & Development, Merck & Co., Inc., Rahway, New Jersey 07065, United States.
Hydrogen isotopically labeled compounds have extensive utility across diverse domains, especially in drug discovery and development. However, synthesis of the labeled compounds with exclusive site selectivity and/or high isotope incorporation is challenging. One widely employed method is heterogeneous palladium(0)-catalyzed (such as Pd/C) dehalogenative deuteration and tritiation with D/T gas.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, California 92037, United States.
Despite recent advances in ligand-enabled C(sp)-H functionalization of native substrates, controlling chemoselectivity in the presence of methyl and methylene C(sp)-H bonds remains a significant challenge. Herein, we report the first example of the Pd(II)-catalyzed chemoselective lactonization of γ-methyl and methylene C(sp)-H bonds of carboxylic acids. Exclusive chemoselectivity of methyl or methylene γ-lactonization was achieved by using two different classes of Quinoline-Pyridone ligands.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Key Laboratory of Molecule Synthesis and Function Discovery, Fujian Province University, College of Chemistry at Fuzhou University, Fuzhou, Fujian, 350108, China.
Zweifel reaction is a powerful strategy to construct olefins from alkenyl tetracoordinate borons in organoboron chemistry, however, it usually only involves one functional group migration and then undergoes an elimination process affording alkenes or alkynes exclusively. Herein, we disclose several intriguing interception of alkynyl tetracoordinate borons with sulfur electrophiles. Wherein, the substituted benzothiophenes are accessed by consecutive 1,2-migrations and intramolecular electrophilic substitution, meanwhile, the challenging and elusive five/four-membered boracycles are easily assembled, and an approach to alkenyl sulfides with good stereoselectivity was developed as well.
View Article and Find Full Text PDFJ Chem Educ
August 2024
Otto-Diels-Institut für Organische Chemie, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany.
Isotopic labeling is an important tool in medicinal research, metabolomics, and for understanding reaction mechanisms. In this context, transition metal-catalyzed C-H activation has emerged as a key technology for deuterium incorporation via hydrogen isotope exchange. A detailed and easy-to-implement experimental procedure for a nondirected arene deuteration has been developed that exclusively uses commercial equipment and chemicals.
View Article and Find Full Text PDFChemistry
July 2024
University of Coimbra, CQC-IMS, Department of Chemistry, 3004-535, Coimbra, Portugal.
Probing quantum mechanical tunneling (QMT) in chemical reactions is crucial to understanding and developing new transformations. Primary H/D kinetic isotopic effects (KIEs) beyond the semiclassical maximum values of 7-10 (room temperature) are commonly used to assess substantial QMT contributions in one-step hydrogen transfer reactions, because of the much greater QMT probability of protium vs. deuterium.
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