Highly Efficient Atom Transfer Radical Addition Reactions with a Ru^III Complex as a Catalyst Precursor

Abstract

The combination of the air-stable RuIII complex [Cp*RuCl2(PPh3)] with AIBN can be used to catalyze the atom transfer radical addition reactions of polychlorinated compounds and of sulfonyl chlorides to olefins with unprecedented turnover numbers of up to 44 000.

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

“…In addition, Severin and co-workers have proposed a methodology to improve the catalytic activity of ruthenium half-sandwich complexes, which consisted in the addition of the radical initiator azobis(isobutyronitrile) (AIBN) as cocatalyst. [34] Such additive continuously regenerates the lower oxidation state of the [Cp*RuCl(PPh3)2] complex. As a result, an exceptionally increase in yields were observed.…”

Copper‐Catalyzed Synthesis of 1,2‐Disubstituted Cyclopentanes from 1,6‐Dienes by Ring‐Closing Kharasch Addition of Carbon Tetrachloride

“…Such behavior leads to accumulation of the Cu(II) species, and therefore the initiating Cu(I) species cannot be regenerated, therefore diminishing the catalytic activity. This same proposal was made by Severin and co-worker [29] for a Ru(II)-based system for ATRA reactions, in which accumulation of RuA C H T U N G T R E N N U N G (III) À Cl complexes induced a decrease of the catalytic rates. This problem is also of relevance in copper-catalyzed ATRP systems, for which Matyjaszewski et al have recently introduced the concept of initiators for continuous activator regeneration (ICAR).…”

“…The respective reaction rates for these processes are k C and k l , respectively. It has been already proposed for the organostannane-mediated [29] cyclization of 6-hepten-2-radicals that an oxygen-containing radical affords a higher k C /k l than the methylene one, and the former cyclizes much more rapidly than the later. This process seemed to be independent of the concentration of the species I but dependent of the nature of the radical.…”

Synthesis of poly(di[methylamine]ethyl methacrylate)‐b‐poly(cyclohexyl methacrylate)‐b‐poly(di[methylamine]ethyl methacrylate) amphiphilic triblock copolymers by ATRP: Condensed‐phase and solution properties

“…[1][2][3][4][5][6][7][8] This polymerisation can be initiated with different alkyl halides, 5,6,[9][10][11][12][13] sulfonyl halides, [14][15][16][17] and N-halides, 18,19 diverse catalyst/ligand systems, [20][21][22][23][24][25][26] and can be carried out in organic and aqueous media [5][6][7][8][9][10][11][12][13][14]27 as well as in carbon dioxide, ionic liquids, or other solvent of low volatility 18,28,29 principally for styrene, meth (acrylate), and acrylonitrile monomers. Its success is due to the effective minimization of termination and chain transfer reactions, which allows developing a great variety of molecular architectures and functionalities with controlled molecular weights and low polydispersities.…”