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Pnictogen bonding (PnB) has gained recognition as an appealing strategy for constructing novel architectures and unlocking new properties. Within the synthetic community, the development of a straightforward and much simpler protocol for cross-electrophile C-P coupling remains an ongoing challenge with organic halides. In this study, we present a simple strategy for photoinduced PnB-enabled cross-electrophile C-P couplings using readily available chlorophosphines and organic halides via merging single electron transfer (SET) and halogen atom transfer (XAT) processes. In this photomediated transformation, the PnB formed between chlorophosphines and alkyl amines facilitates the photogeneration of P radicals and α-aminoalkyl radicals through SET. Subsequently, the resulting α-aminoalkyl radicals activate C-X bonds via XAT, leading to the formation of carbon radicals. This methodology offers operational simplicity and compatibility with both aliphatic and aromatic chlorophosphines and organic halides.
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http://dx.doi.org/10.1002/anie.202310764 | DOI Listing |
Dalton Trans
September 2025
Department of Chemistry and Protein Research Center for Bio-Industry, Hankuk University of Foreign Studies, Yongin 17035, Republic of Korea.
The nanoscale environment within the void spaces of metal-organic frameworks (MOFs) can significantly influence the photoredox catalytic activity of encapsulated visible-light photoredox catalysts (PCs). To compare two isostructural PC@In-MOF systems, three cationic Ru(II) polypyridine complexes were successfully encapsulated within the mesoscale channels of the anionic framework of InTATB (HTATB = 4,4',4''--triazine-2,4,6-triyltribenzoic acid), which features a doubly interpenetrated framework structure. This encapsulation yielded three heterogenized visible-light PCs, RuL@InTATB, where L = 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), or 2,2'-bipyrazine (bpz).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
Shenzhen Grubbs Institute, Department of Chemistry, Guangming Advanced Research Institute, and Shenzhen Key Laboratory of Cross-Coupling Reactions, Southern University of Science and Technology, Shenzhen, 518055, China.
Despite the widespread utility of transition metal-catalyzed cross-couplings in organic synthesis, the coupling of unactivated alkyl electrophiles remains challenging due to sluggish oxidative addition and competing side reactions. Here, we describe a general and practical copper-catalyzed radical deoxyalkynylation of α-unfunctionalized alcohols through a synergistic combination of Barton-McCombie deoxygenation and copper-catalyzed radical cross-coupling. Key to the success of this method lies in not only the development of rigid anionic multiple N,N,N-ligand to exert remarkable selectivity of highly reactive unactivated alkyl radicals, but also the selection of one suitable oxidant to suppress Glaser homocoupling and other side products.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
Cross-electrophile coupling (XEC) reactions are considered to be among the most fundamental construction of carbon-carbon bonds in organic chemistry. Traditionally, stoichiometric reductants, including metallic and organic reagents, are required to promote these conversions, resulting in significant waste that contributes to environmental pollution and increased disposal costs. In this study, we report a divided electrochemical synthesis-based cross-coupling platform in which HO is oxidized at the anode surface to generate electrons that produce a lower oxidation state nickel catalyst on the cathode surface, enabling XEC reactions without the need for metallic or organic reagents.
View Article and Find Full Text PDFInorg Chem
September 2025
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Organic-inorganic hybrid thiocyanates include a variety of compositions and structure types. To develop a better understanding of the interactions that control the crystal structure in this family of materials, six hybrid thiocyanate halide compounds with the general formula ACd(SCN)X (A = CHNH, CHCHNH, CH(CH)NH, CH(CH)NH; X = Cl, Br) have been synthesized. Single crystal X-ray diffraction shows that five of the six compounds crystallize with triclinic 1̅ symmetry, the lone exception being (CH(CH)NH)Cd(SCN)Cl which adopts 2/ symmetry.
View Article and Find Full Text PDFACS Appl Mater Interfaces
September 2025
TOSOH SGM Corp., 4555, Kaisei-cho, Shunan, Yamaguchi 746-0006, Japan.
This study presents a simple method for embedding inorganic-organic hybrid lead halide perovskite (CHNH)PbX (X = Cl, Br, or I) nanocrystals (NCs) into the interlayer spaces of the layered polysilicate kenyaite. (CHNH)PbX NC-embedded kenyaite composites (MPX@kenyaite) were synthesized by immersing Pb-containing kenyaite in (CHNH)X-containing 2-propanol. According to X-ray diffraction, small-angle X-ray scattering, and scanning transmission electron microscopy analyses, (CHNH)PbX NCs with diameters of 5.
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