The C-H imidation of arenes and heteroarenes has been achieved via visible light induced photocatalysis. In the presence of an iridium(III) photoredox catalyst, the reaction of aromatic substrates with N-chlorophthalimide furnishes the N-aryl products at room temperature through a nitrogen-centered radical mediated aromatic substitution.
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http://dx.doi.org/10.1039/c4cc03905j | DOI Listing |
ACS Appl Mater Interfaces
January 2025
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China.
As an efficient, sustainable, and environmentally friendly semiconductor material, covalent organic frameworks (COFs) can generate hydrogen peroxide (HO) by photocatalysis, attracting wide attention in recent years. Herein, the effects of hydroxyl, methoxyl, and vinyl groups of imide-linked two-dimensional (2D) COFs on the photocatalytic production of HO were studied theoretically and experimentally. The introduction of vinyl groups greatly promotes the photogenerated charge separation and migration of COFs, providing more oxygen adsorption sites, stronger proton affinity, and lower intermediate binding energy, which effectively facilitates the rapid conversion of oxygen to HO.
View Article and Find Full Text PDFJ Org Chem
January 2025
School of Traditional Chinese Medicine, Southern Medical University, Guangzhou 510515, China.
The first Ru(II)-catalyzed C-H activation/[4 + 2] annulation of aryl imidates with heteroaromatic iodonium ylides is reported. Our approach features the utilization of a commercially available ruthenium catalyst, providing a one-step construction of phelligridin analogues from easily available and nonpreactivated starting materials. The developed methodology is successfully employed for the total synthesis of phelligridin A, significantly streamlining previous multistep synthesis.
View Article and Find Full Text PDFOrg Lett
October 2024
Key Laboratory of Catalytic Conversion and Clean Energy in Universities of Shandong Province, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, P. R. China.
Transition-metal-catalyzed C-H activation has proven to be a powerful tool for the late-stage modification of peptides. We herein report a method for site-selective alkylation of peptides with maleimides through Pd-catalyzed β-C(sp)-H activation. In this protocol, the methionine residues within peptides serve as the directing groups, which circumvented the preinstallation and subsequent removal of the directing groups.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA-02139, USA.
Main-group element-mediated C-H activation remains experimentally challenging and the development of clear concepts and design principles has been limited by the increased reactivity of relevant complexes, especially for the heavier elements. Herein, we report that the stibenium ion [(CDC)Sb][NTf] (1) (CDC=bis-pyridyl carbodicarbene; NTf=bis(trifluoromethanesulfonyl)imide) reacts with acetonitrile in the presence of the base 2,6-di-tert-butylpyridine to enable C(sp)-H bond breaking to generate the stiba-methylene nitrile complex [(CDC)Sb(CHCN)][NTf] (2). Kinetic analyses were performed to elucidate the rate dependence for all the substrates involved in the reaction.
View Article and Find Full Text PDFOrg Lett
September 2024
Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, P. R. China.
A tunable Rh(III)-catalyzed C(sp)-H bond functionalization of aryl imidates with cyclic 1,3-diones was developed. With suitable and straightforward reaction condition adjustments, the C-H bond functionalization of diverse aryl imidates with cyclic 1,3-diones occurred smoothly and precisely at room temperature. Accompanied by different directing group transformations, a series of corresponding aryl nitriles, hydrophenanthridin-1(2)-ones, spiro isoindoles, or hydrophenanthridine-1,6(2,5)-diones were synthesized in good yields to provide a rational directing group utilization strategy for the Rh(III)-catalyzed C(sp)-H bond activation.
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