Free-radical additions to olefins in the presence of redox systems

Highly Efficient Copper‐Mediated Atom‐Transfer Radical Addition (ATRA) in the Presence of Reducing Agent

“…The mechanism is modified from the well established free radical mechanism operating in metal-catalyzed ATRA reactions. [7,[31][32][33][34] In order to increase the chemoselectivity towards the monoadduct, the following general guidelines need to be met: (a) radical concentration must be low in order to suppress radical termination reactions [activation rate constant (k a,1 and k a,2 ) ϽϽ deactivation rate constant (k d,1 and k d,2 )], (b) further activation of the monoadduct should be avoided (k a,1 ϾϾ k a,2 ) and (c) the formation of oligomers/polymers should be suppressed {rate of transfer…”

Cyclic voltammetric studies of copper complexes catalyzing atom transfer radical polymerization

“…Atom Transfer Radical Addition (ATRA) [1][2][3][4] and Atom Transfer Radical Polymerization (ATRP) [5][6][7][8] are two powerful synthetic methods in organic chemistry and polymer chemistry, respectively. In ATRA, R-X (usually an organic halide) adds across the unsaturated carbon-carbon bond of an alkene, M, to form the monoadduct R-M-X in high yield, while ATRP achieves controlled/"living" radical polymerization of vinyl monomers by the repetitive ATRA process to form R-(M) n -X, as shown in Scheme 1.…”

Photochemical oxidation of methyldiethanolamine (MDEA) in aqueous solution by UV/K2S2O8 process

“…Sulfate radicals show a higher standard reduction potential than hydroxyl radicals at neutral pH, and both radicals show similar reduction potentials under acidic conditions [27]. In general, SO 4 -is more likely to participate in electron transfer reactions, whereas OH is more likely to participate in hydrogen abstraction or addition reactions [32].…”