54648-79-2Relevant articles and documents
Metal-Free and Alkali-Metal-Catalyzed Synthesis of Isoureas from Alcohols and Carbodiimides
Imberdis, Arnaud,Lefèvre, Guillaume,Thuéry, Pierre,Cantat, Thibault
supporting information, p. 3084 - 3088 (2018/02/26)
The first addition of alcohols to carbodiimides catalyzed by transition-metal-free compounds employs 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and its alkali metal salts. Isoureas are obtained in short reaction times and high yields when TBDK is used as the catalyst. Control of the coordination sphere of potassium with exogenous chelating ligands, in combination with mechanistic DFT calculations, demonstrated the role and positive influence of the alkali-metal cation on the kinetics.
Actinide complexes possessing six-membered N-heterocyclic iminato moieties: Synthesis and reactivity
Ghatak, Tapas,Fridman, Natalia,Eisen, Moris S.
, p. 1296 - 1302 (2017/05/29)
A novel class of ligand systems possessing a sixmembered N-heterocyclic iminato [perimidin-2-iminato (PrRN, where R = isopropyl, cycloheptyl)] moiety is introduced. The complexation of these ligands with early actinides (An = Th and U) results in powerful catalysts [(PrRN)An(N{SiMe3)2}3] (3-6) for exigent insertion of alcohols into carbodiimides to produce the corresponding isoureas in short reaction times with excellent yields. Experimental, thermodynamic, and kinetic data as well as the results of stoichiometric reactions provide cumulative evidence that supports a plausible mechanism for the reaction.
Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides
Batrice, Rami J.,Kefalidis, Christos E.,Maron, Laurent,Eisen, Moris S.
supporting information, p. 2114 - 2117 (2016/03/05)
The unprecedented actinide-catalyzed addition of alcohols to carbodiimides is presented. This represents a rare example of thorium-catalyzed transformations of an alcoholic substrate and the first example of uranium complexes showing catalytic reactivity with alcohols. Using the uranium and thorium amides U[N(SiMe3)2]3 and [(Me3Si)2N]2An[κ2-(N,C)-CH2Si(CH3)2N(SiMe3)] (An = Th or U), alcohol additions to unsaturated carbon-nitrogen bonds are achieved in short reaction times with excellent selectivities and high to excellent yields. Computational studies, supported by experimental thermodynamic data, suggest plausible models of the profile of the reaction which allow the system to overcome the high barrier of scission of the actinide-oxygen bond. Accompanied by experimentally determined kinetic parameters, a plausible mechanism is proposed for the catalytic cycle.