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A manganese(II)-catalyzed anti-Markovnikov addition of diarylphosphine oxides to primary and secondary allylic alcohols has been developed, which delivered synthetically valuable γ-hydroxy phosphine oxides. The reaction proceeds under mild, base-assisted conditions with a broad substrate scope and excellent functional group tolerance. Mechanistic studies indicate the involvement of a homogeneous catalytic system and a radical pathway. The reaction is devoid of side products, retains the hydroxy motif, and enables late-stage derivatization, offering an atom-economical approach to organophosphorus compounds.
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http://dx.doi.org/10.1021/acs.orglett.5c03456 | DOI Listing |
Org Biomol Chem
September 2025
Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Herein, we report a simple, microwave-assisted and open-air strategy for gram-scale C3-alkylation of indoles, along with an economically viable strategy for epoxide opening followed by α-alkylation, using the [RuCl(bpy){-PhPCHCONCHPPh-}-κ-(,,,,)] complex (hereafter referred to as [PNP-Ru]). This transformation proceeds an alcohol dehydrogenation (oxidation) mechanism, with water being the sole byproduct in both reactions, underscoring the environmentally benign and sustainable nature of the methodology. The protocol efficiently delivers both mono- and bis(indolyl) derivatives in good to excellent yields.
View Article and Find Full Text PDFAnal Chim Acta
November 2025
Chemical and Veterinary Investigations Office Stuttgart, Schaflandstraße 3/2, 70736, Fellbach, Germany.
Background: Previous studies involving cleanup via conventional solid-phase extraction (SPE) materials to overcome matrix effects for the polar organophosphonate and -phosphinate pesticides glyphosate, glufosinate, ethephon, fosetyl, and their various metabolites often showed limitations due to the existence of various matrix compounds in plant commodities with similar polarity. To overcome existing drawbacks, we utilized the unique selectivity provided by metal oxides as SPE materials. These were exploited in a novel automated online SPE-LC-MS/MS method which allowed analyte-specific trapping in the presence of excessive amounts of matrix compounds as typically contained in extracts of the Quick Polar Pesticides (QuPPe) method.
View Article and Find Full Text PDFOrg Lett
September 2025
School of Chemical Sciences, National Institute of Science Education and Research (NISER), An OCC of Homi Bhabha National Institute, Bhubaneswar 752050, India.
A manganese(II)-catalyzed anti-Markovnikov addition of diarylphosphine oxides to primary and secondary allylic alcohols has been developed, which delivered synthetically valuable γ-hydroxy phosphine oxides. The reaction proceeds under mild, base-assisted conditions with a broad substrate scope and excellent functional group tolerance. Mechanistic studies indicate the involvement of a homogeneous catalytic system and a radical pathway.
View Article and Find Full Text PDFDalton Trans
September 2025
College of Chemistry, Beijing Normal University, No. 19, Xin-wai street, Beijing 100875, People's Republic of China.
The design of multidentate ligands incorporating both hard and soft donors is of fundamental interest and importance in coordination chemistry. Here, we report a novel class of tetradentate dianionic bisphenolate-bisphosphine (PO) ligands featuring hybrid hard (phenolate) and soft (phosphine) donor atoms. Titanium(IV) and titanium(III) chloride complexes of the PO ligands were synthesized and characterized by X-ray crystallography, NMR spectroscopy, solution magnetic susceptibility measurements (Evans method) and EPR spectroscopy, revealing distorted octahedral geometries and providing insight into coordination modes and spin states.
View Article and Find Full Text PDFJ Org Chem
September 2025
Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Zhejiang Key Laboratory of Organosilicon Material Technology, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, Zhejiang 311121, China.
A photoinduced palladium-catalyzed radical C(sp)-H phosphinoylation of tetrahydroisoquinoline was reported. Easily accessible and inexpensive Cl-phosphine oxides were employed as phosphorus radical sources. The key steps in this strategy involve the generation of phosphorus and carbon radicals using the excited palladium complex.
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