Cu-I-catalyzed aerobic oxidation of tertiary amines as the substrate involves active radicals as the oxidized intermediates, in which the reduced intermediates, Cu-I complexes, play a role of oxygen carriers to activate O-2 into the proton/electron/hydrogen-atom acceptor, while tertiary amines serve as the corresponding donor and afford alpha aminoalkyl carbon-centered radicals. Cu-I-catalyzed oxidation ofvarious tertiary amines using aerobic O-2 diffused from air as the ultimate oxidant and air-stable Cu-II salts as the catalyst precursor was adopted as the chain initiation for radical polymerization of methyl methacrylate (MMA) in dimethylsulfoxide at 90 degrees C. The polymerization kinetics was monitored by gas chromatography, while the molecular weight and stereotacticity of PMMA were determined by gel-permeation chromatography and nuclear magnetic resonance spectroscopy. Triethylamine behaved as an efficient substrate while Cu-II/2,2'-bipyridine complexes displayed a higher catalytic activity. The polymerization proceeded in a conventional fashion at a comparable rate even using several micromol of Cu-II/2,2'-bipyridine complexes per liter, leading to syndiotactic-rich PMMA (syndiotacticity >55%) with an alpha-amino terminal moiety as the residue from the tertiary amine substrate, which was confirmed by UV-induced benzophenone-initiated radical polymerization using the so-obtained PMMA as the macro-sensitizer. The catalyst-performance analysis suggested that each molecule of Cu-II/2,2'-bipyridine complexes could generate 3 x 10(2) propagating PMMA(center dot) radicals in 3 h under optimal conditions. (C) 2016 Elsevier B.V. All rights reserved.