Isolable cyclic (alkyl)(amino)carbene–phosphonyl radical adducts

Isolable cAAC–phosphonyl radical adducts were prepared; interestingly, some of them show typical phosphorus-centered radical reactivity under UV irradiation.

Evaluation of Transition Metal Catalysts in Electrochemically Induced Aromatic Phosphonation

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.

Manganese(iii)-mediated alkenyl Csp2–P bond formation from the reaction of β-nitrostyrenes with dialkyl phosphites

Mn(OAc)3-mediated tandem phosphonyl radical addition to β-nitrostyrenes followed by denitration to form (E)-2-alkenyl phosphonates is described.

Novel regio- and stereoselective phosphonyl radical addition to glycals promoted by Mn(ii)–air: syntheses of 1,2-dideoxy 2-C-diphenylphosphinylglycopyranosides

The novel Mn(ii)–air promoted radical reaction of diphenylphosphine oxide with various glycals in excellent regio- and stereoselectivities generated 1,2-dideoxy-2-C-diphenylphosphinylglycopyranosides.