Alkenes homolytic radical additions

Additions. Homolytic bimolecular addition reactions of carbon-centered radicals to unsaturated groups have been studied in detail because these are the reactions of synthesis and polymerization. Within this group, radical additions to substituted alkenes are by far the best understood. An excellent compilation of rate constants for carbon radical additions to alkenes is recommended for many specihc kinetic values. ... 

Houk and coworkers investigated the diastereofacial selectivity in radical additions of substituted cyclohexyl radicals to alkenes [13]. In this work, the force field developed by Spellmeyer and Houk was applied to intermolecular homolytic addition with success and demonstrated the added versatility of the HS model over the BS procedure which is limited to intramolecular systems. Extraordinarily accurate predictions of diastereoselectivity were made. For example, acrylonitrile is predicted to react with the 4-ter -butyl-2-methylcyclohexyl radical 28 to alford the products... 

The only way to produce the observed product is to decompose the diazonium salt homolytically. To do this we can draw the salt as a covalent compound or transfer one electron from the chloride ion to the diazonium salt. The other product would be a chlorine radical. Addition to the alkene gives the more stable radical which abstracts chlorine from the diazonium salt and keeps the chain going. 

Radical addition to alkenes (Section 10.10) A process by which an atom with an unshared electron, such as a bromine atom, adds to an alkene with homolytic cleavage of the tr-hond and formation of a (T-bond from the radical to the carhon the resulting carhon radical then continues the chain reaction to product the final product plus another species with an unshared electron. 

Whereas additions of carbon radicals to alkene moieties are the best characterized homolytic additions, carbon radicals are known to add to a wide range of unsaturated systems. These include polyenes, alkynes, arenes, heteroarenes, carbon monoxide,isonitriles, °° ° nitriles, ° imines and derivatives, ° ° aldehydes,nitrones, and thiones. ° Many of these reactions, such as addition of an alkyl radical to a carbonyl group, ° are thermodynamically unfavorable and readily reversible, and they form the basis of composite group-transfer reactions discussed below. 

There are many reagents that add to alkenes only by radical-chain mechanisms. A number of these are listed in Table 10-3. They have in common a relatively weak bond, X—Y, that can be cleaved homolytically either by light or by chemical initiators such as peroxides. In the propagation steps, the radical that attacks the double bond does so to produce the more stable carbon radical. For addition to simple alkenes and alkynes, the more stable carbon radical is the one with the fewest hydrogens or the most alkyl groups at the radical center. 

The stoichiometric oxidation of alkenes by Mn(OAc)3 in acetic acid at 120 °C affords 7-lactones n good yield, via the homolytic addition of carboxymethyl radical to the double bond (equations 104 and 205).504-506... 

Another important homolytic reaction of tin hydrides is the reduction of carbon-halogen bonds the reaction is promoted by initiators and retarded by radical traps (Scheme 13). Reactivity decreases in the sequence X = I > Br > Cl and BusSnH > Bu2SnH2 Ph3SiiH > BuSnH3. Other groups X in RX that can be reduced by tin hydrides include -OC(S)R, SR, SePh, TePh, NC, and NO2. The intermediate radical, R in Scheme 13, can be trapped by additional substances, e.g. alkenes, or may undergo... 

The most important methodology for the aliphatic C-C bond formation via radical reactions is the addition of the radical to an alkene double bond, both inter -and intramolecularly (with the 5-exo-ring cyclisation mode preferred in the latter case). This reaction leads to adduct radicals that must be converted to non-radical products before polymerisations can take place. For this reason, polymerisation is avoided either by intermolecular trapping of adduct radicals or by intramolecular, homolytic bond cleavage. Hydrogen atom donors X-H, heteroatom donors X-Z or electron donors M"+ are used as trapping agents (Scheme 7.1). 

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