C-P bond formation via selective electrocatalytic C-H phosphorylation

Khrizanforov, Mikhail; Strekalova, Sofia; Grinenko, V. V.; Kononov, A. I.; Dolengovski, Egor L.; Budnikova, Yu. G.

doi:10.1080/10426507.2018.1555538

Cited by 1 publication

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“…Earlier, we proposed an electrocatalytic approach for the phosphonation of aromatic, heteroaromatic, and heterocyclic compounds in one stage using transition metal complexes and salts as catalysts (Scheme 2) [33,34,35,36,37,38,39,40,41,42,43]. Successful C–H/P–H cross-coupling of dialkyl- H -phosphonate was shown with different (hetero)aromatic molecules such as benzenes bearing electron donor and electron withdrawing substituents in the aromatic ring; coumarines under electro-oxidation (Scheme 2A) or electroreduction conditions (Scheme 2B) under the action of Ni, Co, or Mn catalysts and the mixtures of metal complexes [33,34,35,36,37,38,39,40,41,42,43]; and azole derivatives (benzo-1,3-azoles, 3-methylindole, 4-methyl-2-acetylthiazole) under the action of Ag + (Scheme 2C) [20]. It is worth mentioning that electro-oxidative coupling of diphenylphosphine oxide with acetylenes in the presence of catalytic amounts of Ag + yielded the formation of benzo[ b ]phosphole oxides [44].…”

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confidence: 99%

Evaluation of Transition Metal Catalysts in Electrochemically Induced Aromatic Phosphonation

2019

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Voltammetry provides important information on the redox properties of catalysts (transition metal complexes of Ni, Co, Mn, etc.) and their activity in electrocatalytic reactions of aromatic C–H phosphonation in the presence of a phosphorus precursor, for example, dialkyl-H-phosphonate. Based on catalytic current growth of oxidation or reduction of the metal catalysts (CoII, MnII, NiII, MnII/NiII, MnII/CoII, and CoII/NiII), quantitative characteristics of the regeneration of catalysts were determined, for example, for MnII, NiII and MnII/NiII, CoII/NiII pairs. Calculations confirmed the previously made synthetic observations on the synergistic effect of certain metal ions in binary catalytic systems (MnIIbpy/NiIIbpy and NiIIbpy/CoIIbpy); for mixtures, the observed rate constants, or TOF, were 690 s−1 and 721 s−1, respectively, and product yields were higher for monometallic catalytic systems (up to 71% for bimetallic catalytic systems and ~30% for monometallic catalytic systems). In some cases, the appearance of pre-waves after adding H-phosphonates confirmed the preceding chemical reaction. It also confirmed the formation of metal phosphonates in the time scale of voltammetry, oxidizing or reducing at lower potentials than the original (RO)2P(O)H and metal complex, which could be used for fast diagnostics of metal ion and dialkyl-H-phosphonate interactions. Electrochemical transfer of an electron to (from) metal phosphonate generates a phosphonyl radical, which can then react with different arenes to give the products of aromatic C–H phosphonation.

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