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The synthesis of a small library of -Boc- or -Fmoc-protected l-phenylalanines carrying methyl groups at positions 2 and 6 and diverse functionalities at position 4 has been achieved. The approach, which took advantage of a Pd-catalyzed directed C-H dimethylation of picolinamide derivatives, allowed the electronic and steric properties of the resulting amino acid derivatives to be altered by appending a variety of electron-withdrawing, electron-donating, or bulky groups.
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http://dx.doi.org/10.1021/acs.joc.1c02527 | DOI Listing |
J Am Chem Soc
September 2025
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
The C-H functionalization of arenes mediated by well-defined bis(phosphine)-supported organometallic iron(III) complexes is described. One-electron oxidation of -(depe)Fe(CH) (depe = 1,2-bis(diethylphosphino)ethane) generated the corresponding isolable iron(III) dimethyl derivative that was unstable toward Fe-CH homolysis. Oxidation of the corresponding iron(II) bis(aryl) complex -(depe)Fe(tolyl) resulted in rapid reductive elimination of the biaryl with formation of iron(I).
View Article and Find Full Text PDFSci Rep
August 2025
Laboratory of Organic Synthesis and Natural Products, Department of Chemistry, Sharif University of Technology, Azadi Street, 111559516, Tehran, Iran.
In this study, we introduce a protocol for the methylation of the C-H bond at the C position in imidazo[1,2-a]pyridine scaffolds, employing magnetic def./Cu-MOF for the activation of C(sp2)-H bonds. The term 'def' refers to strategically induced defects in the Metal-Organic Framework (MOF), which are designed to improve its catalytic efficiency.
View Article and Find Full Text PDFOrg Lett
August 2025
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan.
Conformers can interconvert when the transition state lies sufficiently low in energy. Nevertheless, the transition-state geometry is minimally populated or intrinsically unpopulated in solution, making its isolation in the solid state extremely challenging. A tetraaza derivative of anthraquinodimethane bearing vicinal dimethyl groups exhibits high conformational flexibility.
View Article and Find Full Text PDFJ Phys Chem A
August 2025
Chemistry and Chemical Engineering Guangdong Laboratory, Shantou 515031, China.
Glycerol can be efficiently converted to dihydroxyacetone using organometallic Pd catalysts. However, the entire catalytic cycle and reaction mechanism have not been comprehensively studied. In this work, we performed detailed theoretical calculations of the mechanism of glycerol conversion to dihydroxyacetone catalyzed by the Pd/2,9-dimethyl-1,10-phenanthroline complex.
View Article and Find Full Text PDFJ Org Chem
July 2025
The State Key Laboratory of Applied Organic Chemistry, and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China.
Herein, we report a visible-light-induced -selective C-H hydroxylation of benzils, which exhibits good functional group tolerance and excellent regioselectivity. This method is scalable, as demonstrated by gram-scale experiments, and is further applied in the synthesis of rotenoids. Control experiments reveal the involvement of singlet oxygen in the reaction mechanism.
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