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This study describes an efficacious and generally applicable synthetic strategy for the incorporation of biologically and physiologically prominent difluoromethyl entity into synthetically crucial hydrazone scaffolds with bench-stable and easily accessible difluoromethyltriphenylphosphonium bromide. The broad substrate scope, excellent functional group compatibility, feasibility of step and atom economical one-pot synthetic manipulation, and environmentally benign and mild reaction conditions rendered this methodology an efficient tool for the preparation of synthetically and pharmaceutically prominent fluorine-containing imino compounds.
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http://dx.doi.org/10.1021/acs.orglett.5c00827 | DOI Listing |
Org Lett
September 2025
State Key Laboratory of Natural Product Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China.
A photoredox approach is described for converting dehydroalanine (Dha) residues in peptides to aspartic acid (Asp). Using ammonium formate as a CO radical source under mild conditions, Dha is functionalized in a traceless manner.The protocol is compatible with peptide substrates, including fully unprotected, the complex antimicrobial peptide nisin.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, 350002, P.R. China.
The synthesis of medium-ring lactams constitutes a formidable yet pivotal frontier in modern chemical research. Persistent endeavors in this field are essential for overcoming the prevailing obstacles, particularly in the realm of ring expansion strategies for unstrained cyclic amines. In this study, we introduce a groundbreaking photoredox-catalyzed radical relay process that accomplishes direct C─N bond cleavage in unstrained cyclic amines, thereby enabling the efficient construction of highly functionalized 9-11-membered lactams adorned with a Z-olefin moiety.
View Article and Find Full Text PDFJ Org Chem
August 2025
School of Pharmaceutical and Chemical Engineering, Taizhou University, 1139 Shifu Road, Taizhou 318000, China.
A new method to synthesize α-CFH carbinols has been developed through the photoredox-catalyzed direct radical hydromonofluoromethylation of benzils/isatins, 9-fluoren-9-one, 2-methylisoindoline-1,3-dione, etc., using bench-stable HCFSONa. It was further applied to the synthesis of a bioactive isatin-derived molecule.
View Article and Find Full Text PDFChem Asian J
July 2025
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, 781039, India.
The rapid development of photo-synergistic transition metal catalysis has emerged as a green paradigm to complement thermal transition metal catalytic strategies. The interplay between photoredox and transition metal catalytic cycles allows for precise control over reactivity and selectivity, facilitating the construction of complex molecules, with the formation of diverse C─C, C-heteroatom bonds. Among different transition metal catalysts, copper, abundant in the Earth's crust, is particularly notable for its unique electronic structure and light-absorbing properties.
View Article and Find Full Text PDFOrg Lett
August 2025
Organic Chemistry Division, CSIR-National Chemical Laboratory, Pune 411008, India.
The synthesis of anilides with a chiral C(═O)-N axis has relied on direct installation of the chiral C(sp)-N(sp) bond or enantioselective modification of the peripheral groups. However, these methods are constrained by the size and type of functional groups compatible with each strategy. Herein, we report a dynamic kinetic asymmetric transformation (DYKAT) for the aerobic oxidation of iminium ions to access C(═O)-N axial chirality that addresses those limitations.
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