Copper-catalyzed additions of organic polyhalides to olefins: a versatile synthetic tool

Abstract

Abstract

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.…”

Structural and Mechanistic Aspects of Copper Catalyzed Atom Transfer Radical Polymerization

“…High chemoselectivity of the monoadduct was achieved by recognizing that transition metal complexes are more effective halogen transfer agents than alkyl halides. Complexes of copper [8,9,10,11,12] , iron [8,13,14,15] , ruthenium [16,17,18] , and nickel [19,20,21] were found to be particularly active catalysts for ATRA. Apart from controlling product distribution, great progress has also been made in utilizing a variety of halogenated compounds (alkyl and aryl halides [22,23,24] , N -chloroamines [24] , alkylsulfonyl halides [8,25,26,27,28,29] , and polyhalogenated compounds [8,14,29,30] ), as well as alkenes (styrene, alkyl acrylates, and acrylonitrile).…”

Ligand Effects on the Reactivity of CuIL Complexes Towards Cl3CCO2−

“…The results are presented in Figure 2. The results demonstrate that the rate decreases as the concentration of acetonitrile is increased and seems to approach a limiting value, at [CH 3 …”

“…In principle the addition of appropriate ligands for Cu I , e.g. CH 3 CN, [4] alkenes [5] and NH 3 [5] increases the concentration of the Cu I species in the system and is therefore expected to increase the rate of the catalytic process. Triand tetradentate ligands, which stabilize Cu I , were indeed shown to accelerate catalytic processes.…”