79937-92-1Relevant articles and documents
Unprecedented Copper(II) Complex with a Topoquinone-like Moiety as a Structural and Functional Mimic for Copper Amine Oxidase: Role of Copper(II) in the Genesis and Amine Oxidase Activity
Jangir, Ritambhara,Ansari, Mursaleem,Kaleeswaran, Dhananjayan,Rajaraman, Gopalan,Palaniandavar, Mallayan,Murugavel, Ramaswamy
, p. 10940 - 10950 (2019/11/13)
Copper amine oxidase (CAO), consisting of the topoquinone (TPQ) cofactor, catalyzes the oxidation of primary amines to aldehyde. We have successfully addressed this issue through isolation of a copper complex which mimics the active-site structure as well as the function of CAO. This inimitable complex, consisting of two TPQ-like side-arms, formed by ambient aerial oxidation of a precursor Schiff base complex, is the most efficient homogeneous catalyst for quantitative oxidation of primary benzylic amines to corresponding secondary imines under ambient conditions within 30 min. The longstanding contention of actual involvement of Cu(II) in the catalysis is resolved through quenching experiments of Cu(II) superoxo species and detailed density functional theory studies.
THERMODYNAMIC DISSECTION OF SOLVENT EFFECTS IN THE SCHIFF REACTION
Arcoria, Antonino,Cipria, Antonio,Longo, Maria Luisa,Maccarone, Emanuele,Tomaselli, Gaetano Andrea
, p. 723 - 730 (2007/10/02)
Rate constants for the reactions of p-substituted benzaldehydes with aniline and some 2-alkyl- and 2,6-dialkylanilines to give imines have been measured in acetonitrile and N,N-dimethylformamide at 25 and 75 deg C.The contributions of solvation energies to the free energy of activation have been measured at 25 deg C in cyclohexane, carbon tetrachloride, methanol, N,N-dimethylformamide, acetonitrile, ethylene glycol, dimethyl sulphoxide and N-methylformamide for the reaction of benzaldehyde and aniline.The observed reactivity depends on both polar and steric effects of the alkyl groups.Thermodynamic dissection of solvent effects points out that acidic or basic properties of solvents are important features in determining the rate of the process.However, the changeover of the rate-limiting step from the formation of the intermediate α-amino alcohol (with electron-donating groups) to its dehydration (with electron-withdrawing substituents) seems scarcely affected by solvent variations. 1H NMR measurements in dimethyl sulphoxide allowed the detection of the intermediate α-amino alcohol.
