Elimination, radical alkene

The reactions of alkyl halides with Fe(II) deuteroporphyrin IX have been examined (Wade and Castro 1973). Three classes of reaction were observed (i) hydrogenolysis, (ii) elimination to alkenes, and (iii) coupling of alkyl free radicals. Further discussion has been given in Castro (1998). 

The driving force of the reaction is the formation of a more stable radical, i.e. the unpaired electron is delocalised more effectively by Q in (1276) than by H in (127a). Migration of fluorine does not occur as its d orbitals are not accessible, and migration of Br only rarely as the intermediate radicals undergo elimination (to alkene) more readily than rearrangement. 

While carbon and oxygen radicals add irreversibly to carbon-carbon double bonds, the fragmentation reaction is rapid (and often reversible) for elements like tin, sulfur, selenium and the halogens (Scheme 36). This elimination reaction can be very useful in synthesis if the eliminated radical Y- can either directly or indirectly react with a radical precursor to propagate a chain. Given this prerequisite, an addition chain can be devised with either an allylic or a vinylic precursor, as illustrated in Scheme 37. Carbon radicals are generated by the direct or indirect reaction with Y- and are removed by the -elimination of Y-. Selectivity is determined by the concentration of the alkene acceptor and the rate of -elimination... 

Relatively few alkenes that do not possess some type of activating group react with Sml2-generated alkyl radicals. Alkenes adorned with allylic heterosubstituents have been employed in this capacity [7a]. The heterosubstituents serve to lower the LUMO of the alkene, making it a better radical acceptor. In these systems elimination occurs subsequent to the initial radical addition (Eq. 10). 

Fragmentation Loss of halogen radical (I > Br > Cl > F) followed by elimination of alkenes. Loss of alkyl radical followed by elimination of acid HX. Loss of acid HX to give an alkene radical cation. 

The primary and secondary products of photolysis of common diazirines are collected in Table 4. According to the table secondary reactions include not only isomerization of alkenes and hydrogen elimination to alkynes, but also a retro-Diels-Alder reaction of vibrationally excited cyclohexene, as well as obvious radical reactions in the case of excited propene. 

Aromatic ethers and furans undergo alkoxylation by addition upon electrolysis in an alcohol containing a suitable electrolyte.Other compounds such as aromatic hydrocarbons, alkenes, A -alkyl amides, and ethers lead to alkoxylated products by substitution. Two mechanisms for these electrochemical alkoxylations are currently discussed. The first one consists of direct oxidation of the substrate to give the radical cation which reacts with the alcohol, followed by reoxidation of the intermediate radical and either alcoholysis or elimination of a proton to the final product. In the second mechanism the primary step is the oxidation of the alcoholate to give an alkoxyl radical which then reacts with the substrate, the consequent steps then being the same as above. The formation of quinone acetals in particular seems to proceed via the second mechanism. ... 

When the radicals have p hydrogens, alkenes are formed by a process in which carbocations are probably bypassed. Instead, the oxidation and the elimination of a proton probably occur in a single step through an alkylcopper species. The oxidation state of copper in such an intermediate is Cu(III). 

Stereoselective preparation of CEi-allyl alcohols via radical elimination from ruin -y-phenylthio-fi-nkro alcohols has been reported. The requisiteruin -fi-nitro sulfides are prepared by protonadon of nitronates at low temperanire Isee Chapter 4, and subsequent treatment v/ith Bu-vSnH induces and eliminadon to givelE -alkenes selecdvely IseeEq. 7.112. Unfortunately, it is difficult to get the pure syu-fi-nitro sulfides. Treatment of a rruxnire of syu- and ruin -fi-nitrosulfides v/ith Bu- SnH results in formadon of a rruxnire of (Ey and lZ -alkenes. 

In the dehydration pathway, water is eliminated, yielding an alkene radical cation with a mass 18 units less than M+. 

Romakhin et al. [49] showed that anodically generated phosphoniumyl radicals can add onto alkenes to yield phosphonylated alkenes through an anodic oxi-dation/addition/anodic oxidation/elimination/nucleophilic attack sequence (Scheme 17). 

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