Ruthenium(II)- and rhenium(III)-catalysed addition of tetrahalogenomethanes to alkenes and 1,ω-dienes. Stereoselective formation of cis-1,2-disubstituted cyclopentanes from 1,6-dienes

Diaminoarylnickel(II) “Pincer” Complexes: Mechanistic Considerations in the Kharasch Addition Reaction, Controlled Polymerization, and Dendrimeric Transition Metal Catalysts

“…A number of species were found to initiate free-radical addition of polyhalogenated alkanes to alkenes (cf. peroxides); these include ReCl 3 (PR 3 ) 2 L, 9 AlMe 3 , 10 BMe 3 , 11 M(CO) 6 (M ) Cr, Mo, W), Fe(CO) 5 , 12 and metal dispersions. 13 Telomerization was still a recurring problem, however.…”

Catalytic Synthesis and Antifungal Activity of New Polychlorinated Natural Terpenes

“…The Kharasch addition reaction requires either a free radical precursor as the promoter or a metal complex as the catalyst. The classical free radical chain mechanism is operative not only with initiators such as light, heat, and peroxides [27][28][29] but also with a variety of metal complexes (Scheme 1) [27]. The addition of tetrachloromethane to unsaturated terpenes can be obtained by treatment with CCl 4 , Fe(acac) 2 as catalyst, and NEt 3 in dry acetonitrile at 80 ∘ C. A possible mechanism for Kharasch reaction is shown in Scheme 1.…”

“…The reaction occurs through a "ligand-transfer" mechanism (inner-sphere electron transfer) (Scheme 2) [26][27][28][29].…”

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

“…[12,18,19,20] Mild conditions (30 8C) without the need of irradiation [24] or heat for the generation of the radical species and relatively low charge of catalyst (1%) are employed in our system. After these findings, we focussed our attention in the understanding of this transformation in order to improve the catalytic conversions.…”

“…[5] An interesting transformation is the one leading to the formation of five-membered rings via consecutive Kharasch addition of CCl 4 to 1,6-heptadienes followed by radical cyclization (Scheme 2). This reaction has been shown to be catalyzed by dimanganese decacarbonyl, [12] rhenium, [18] ruthenium, [18,19,20] rhodium [20] and iridium. [20] This reaction usually affords a mixture of compounds from the cyclization (cis and trans isomers) or the simple ATRA reaction onto one or two double bonds.…”