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

Abstract

Transition‐metal‐catalyzed atom transfer radical reactions of halogenated compounds with olefins constitute a versatile tool in organic synthesis within the area of C–C bond forming transformations. The inter‐ or intramolecular versions, atom transfer radical addition (ATRA) or cyclization (ATRC), respectively, lead to the atom‐economic, useful synthesis of compounds that can be further functionalized. This contribution summarizes the recent developments in this area in terms of catalyst design as well as the applicability of this methodology in sequential, domino, or tandem reactions.

Immobilized copper catalyst for atom transfer radical addition and polymerization

“…These side reactions not only decrease the yield in the desired addition products but also induce the accumulation of Cu 2+ , affecting the Cu + /[Cu 2+ ] ratio and finally causing the reduction of the catalytic activity of the catalysts. [24] As for the ATRA of MTCA to St, similar results were obtained. This is also shown in Tables 1 and 2.…”

Tris(2-pyridylmethyl)amine Based Ligands in Copper Catalyzed Atom Transfer Radical Addition (ATRA) and Polymerization (ATRP)

“…Both processes originated from well-known Kharasch addition in which polyhalogenated compounds were added to alkenes via free-radical means (13,39,40). Recent studies have also indicated that TPMA is a superior complexing ligand in ATRA (13,33,40,(44)(45)(46)(47)(48)(49)(50)(51)(52)(53)(54) and ATRP (49,(55)(56)(57)(58) that utilize reducing agents. The role of a reducing agent in both systems is to continuously regenerate the activator species (copper(I) complex) from the corresponding deactivator (copper(II) complex).…”

Towards the development of highly active copper catalysts for atom transfer radical addition (ATRA) and polymerization (ATRP)‡

“…(Eckenhoff & Pintauer, 2010a;Pintauer, 2008Pintauer, , 2009Pintauer, , 2010. Therefore, transition metal catalyzed (TMC) ATRA became a broadly applicable synthetic tool (Clark, 2002;Curran, 1992;De Campo et al, 2000;Eckenhoff & Pintauer, 2010b;Gossage et al, 1998;Muñoz-Molina et al, 2011;Pintauer, 2010;Severin, 2006). Largely based on chemo-, regio-, and stereoselectivity, it is generally accepted that the mechanism of TMC ATRA involves free radical intermediates (Asscher & Vofsi, 1961;Minisci, 1975).…”