The copper(i)-promoted cross-coupling of 1,2-di(pyrimidin-2-yl) disulfides with aromatic amines and aliphatic amines to deliver C-N coupling products in moderate to good yields is reported in this paper. Central to this strategy is the conversion of disulfides into aryl- and alkyl amines by a copper-promoted chemoselective C-S bond cleavage.
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http://dx.doi.org/10.1039/c5ob02535d | DOI Listing |
Biocompatible covalent reactive groups (CRGs) play pivotal roles in several areas of chemical biology and the life sciences, including targeted covalent inhibitor design and preparation of advanced biologic drugs, such as antibody-drug conjugates. In this study, we present the discovery that the small, chlorinated polyketide natural product cyclohelminthiol II (CHM-II) acts as a new type of cysteine/thiol-targeting CRG incorporating both reversible and irreversible reactivity. We devise the first syntheses of four simple cyclohelminthols, (±)-cyclohelminthol I-IV, with selective chlorinations (at C and C) and a Ni-catalyzed reductive cross coupling between an enone, a vinyl bromide and triethylsilyl chloride as the key steps.
View Article and Find Full Text PDFChem Sci
January 2025
Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences Shanghai 200032 China
An efficient Pd-catalyzed regioselective intramolecular aerobic oxidative dehydrocoupling of BH/CH between -carborane and arenes has been achieved with the construction of a series of five-, six- and seven-membered rings under mild reaction conditions. Control experiments indicate that B-H activation proceeds preferentially over the aryl C-H. These new polyarene-carborane conjugates have potential applications in materials as demonstrated by pyrene fused -carborane that exhibits unique dual-phase emission, intramolecular charge transfer (ICT), and aggregation-induced emission (AIE) properties.
View Article and Find Full Text PDFOrganometallics
January 2025
IU CINQUIMA/Química Inorgánica, Universidad de Valladolid, Valladolid 47071, Spain.
The reaction of diphosphino aryl complexes [Pd(CF)(L-L)(NCMe)](BF) (L-L = dppe, dppp, dppb) with diazoalkanes NCHR ( = -CH=CHPh, Ph) leads to η-allyl or η-benzyl palladium derivatives that are the organometallic products resulting from carbene-aryl coupling. The experimental trend shows that the reaction is favored for dppe > dppp > dppb. It involves several consecutive steps, i.
View Article and Find Full Text PDFNat Commun
January 2025
Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, P. R. China.
Metal-centered chirality has been recognized for over one century, and stereogenic-at-metal complexes where chirality is exclusively attributed to the metal center due to the specific coordination pattern of achiral ligands around the metal ion, has been broadly utilized in diverse areas of natural science. However, synthesis of these molecules remains constrained. Notably, while asymmetric catalysis has played a crucial role in the production of optically active organic molecules, its application to stereogenic-at-metal complexes is less straightforward.
View Article and Find Full Text PDFJ Org Chem
January 2025
The Center for Combinatorial Chemistry and Drug Discovery of Jilin University, The School of Pharmaceutical Sciences, Jilin University, 1266 Fujin Road, Changchun, Jilin 130021, P. R. China.
A novel and efficient electrochemical method for electroselective and controlled cross-coupling of isoindolinones with equivalent alcohols has been developed without the need for metal catalysts and strong bases under mild conditions. The reaction provides a novel strategy for the controllable and effective synthesis of 3-alkoxyl and -hydroxymethyl-substituted isoindolinones, which is adjusted by 4-OH-TEMPO and tolerates various substrates. This protocol is an efficient tool for the construction of C-O and C-N bonds with high chemoselectivity.
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