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An efficient arylation of electron-poor arenes has been developed without the addition of external ligands or in the presence of a catalytic monoprotected amino acid which assisted the reaction to proceed under mild conditions. The meta-selectivity was observed under both conditions.
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http://dx.doi.org/10.1039/c2cc34949c | DOI Listing |
J Am Chem Soc
June 2025
Department of Chemistry, The Scripps Research Institute, La Jolla, California 92037, United States.
Enantioselective oxygenation of unactivated C(sp)-H bonds via asymmetric metalation remains an unsolved challenge. Herein we report the development of a Pd-catalyzed, enantioselective C(sp)-H tosylation of native amides with NaOTs as the nucleophile, representing a rare example of enantioselective C-H functionalization with a nucleophilic coupling partner. High enantioselectivity in this reaction is achieved by chiral monoprotected amino sulfonamide (MPASA) ligands.
View Article and Find Full Text PDFChemistry
May 2025
Laboratory of Bioorganic Chemistry and Chemical Biology, Center for Nanotechnology, Heisenbergstrasse 11, 48149, Münster, Germany.
Bioorthogonal functionalization in the minor groove of DNA with protected 2-amino-2'-deoxyadenosine (2-amino-dA, 1) as a target site is described. Cyclopropene and heptene as part of 2-aminoacyl protecting groups served as dienophiles in inverse-electron demand Diels-Alder (iEDDA) reactions with 3,6-dipyridyl-1,2,4,5-tetrazine as diene. For the purpose, bis-protection of 1 with cyclopropenyl and heptenoyl groups was conducted.
View Article and Find Full Text PDFJ Am Chem Soc
February 2025
The Scripps Research Institute (TSRI), 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
A diverse range of Pd(II)-catalyzed enantioselective C-H activation reactions have been developed to construct point, axial, and planar chirality. Despite the importance of chiral biaryl scaffolds in bioactive molecules and chiral ligands, atroposelective functionalization at the -position remains a significant challenge. Here, we realized a rare atroposelective remote -C-H functionalization with a chiral monoprotected amino acid (MPAA) ligand and a racemic transient norbornene mediator.
View Article and Find Full Text PDFChemistry
February 2025
Key Laboratory of Radiopharmaceuticals, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing, 100875, China.
Optically pure monosubstituted [n]paracyclophanes are promising candidates for material synthesis, asymmetric catalysis, and drug discovery. Thus far, only a few catalytic asymmetric synthesis processes have been reported for assessing these strained atropisomers. In this study, we describe a highly enantioselective synthesis of monosubstituted [n]paracyclophanes by combining desymmetrization and kinetic resolution.
View Article and Find Full Text PDFNature
January 2025
Department of Chemistry, The Scripps Research Institute, La Jolla, CA, USA.
C-H activation is the most direct way of functionalizing organic molecules. Many advances in this field still require specific directing groups to achieve the necessary activity and selectivity. Developing C-H activation reactions directed by native functional groups is essential for their broad application in synthesis.
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