Minisci reaction alkenes

The Minisci reaction has successfully been applied for the alkylation of various heteroarenes, i. e. lepidine, pyrazine, quinoline and quinoxaline [2e, 2g, 10]. Organic compounds such as alkanes, alkenes, carboxylic acids, esters, amides, amines, alcohols, ethers, aldehydes, ketones, halides etc. have been successfully used as radical precursors in the Minisci reaction. A good overview of the different methods which have been applied to generate the alkyl radicals in these processes is summarized in [10b]. 

The dependence of relative rates in radical addition reactions on the nucleophilicity of the attacking radical has also been demonstrated by Minisci and coworkers (Table 7)17. The evaluation of relative rate constants was in this case based on the product analysis in reactions, in which substituted alkyl radicals were first generated by oxidative decomposition of diacyl peroxides, then added to a mixture of two alkenes, one of them the diene. The final products were obtained by oxidation of the intermediate allyl radicals to cations which were trapped with methanol. The data for the acrylonitrile-butadiene... 

Minisci, Galli and co-workers have studied a variety of radical reactions which result in the formation of organic azides. These processes commonly involve the interaction of an organic peroxide, an alkene, and azide ion in the presence of a ferrous-ferric redox system. The initial step is the reduction of the peroxide by Fe " " to form a free alkoxy radical (Fenton reaction, equation 104). 

The addition of polyhaloalkanes and related halo-genated compounds to alkenes can occur via a classical radical chain process (Scheme 13), which is often called the Kharasch reaction.38 In 1961, Minisci et al.39 and Asscher and Vofsi40 discovered that this reaction is catalyzed by transition metal ions in their lower valent state such as Cu+ and Fe2+, and they formulated the mechanism in Scheme 14. The catalysis of the additions by simple metal salts or complexes such as Cu(I)-2,2 -bipyridyl41a and ruthe-... 

Atom radical transfer polymerisation (ATRP) has its roots in atom transfer radical addition (ATRA), which involves the formation of 1 1 adducts of alkyl halides and alkenes, and is also catalysed by transition metal complexes. ATRP is a modification of the Kharasch addition reaction (Kharasch et al. 1945) although there may be some differences (Minisci 1975). A general mechanism for ATRP is shown in Scheme 10.5. In ATRP the radicals or the active species are generated through a reversible redox process catalysed by a transition metal complex (Mtn-L/... 

F. Antonietti, A. Mele, F. Minisci, C. Punta, F. Recupero, F. Fontana, Enthalpic and polar effects in the reactions of perfluoroalkyl radicals. New selective synthetic developments with alkenes and heteroaromatic bases, J. Huorine Chem. 125 (2004) 205-211. 

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