Radical cation/anion pairs, electrophilic oxidation

On the basis of kinetic studies, a mechanism for the radical oxidation of thioether with 36 has been proposed and is indicated in Scheme D ". The key step involves the formation of a radical cation-anion pair within the solvent cage. The presence of the pic ligand in the coordination sphere of the metal reduces the electrophilicity of the peroxo complex, thus allowing the competitive radical process to take place. 

The wide diversity of the foregoing reactions with electron-poor acceptors (which include cationic and neutral electrophiles as well as strong and weak one-electron oxidants) points to enol silyl ethers as electron donors in general. Indeed, we will show how the electron-transfer paradigm can be applied to the various reactions of enol silyl ethers listed above in which the donor/acceptor pair leads to a variety of reactive intermediates including cation radicals, anion radicals, radicals, etc. that govern the product distribution. Moreover, the modulation of ion-pair (cation radical and anion radical) dynamics by solvent and added salt allows control of the competing pathways to achieve the desired selectivity (see below). 

The deprotonation step, either by the sensitizer radical anion or by some adventitious base, is essential for the formation of any amine derived products. This step can be prevented if the a-hydrogens are arranged in a plane orthogonal to the singly occupied nitrogen n-orbital a requirement which is met for the radical cation of l,4-diazabicyclo[2.2.2]octane (DABCO). The low oxidation potential, due to the interaction of the pair of transannular nitrogens, makes this an excellent electron transfer quencher. Yet, no product formation is observed as a result of these interactions, with the possible exception of the zwitterionic adducts formed with highly electrophilic ketones [193]. 

Both, strained and unsaturated organic molecules are known to form cation radicals as a result of electron transfer to photoexdted sensitizers (excited-state oxidants). The resulting cation radical-anion radical pairs can undergo a variety of reactions, including back electron transfer, nucleophilic attack on to the cation radical, electrophilic attack on the anion radical, reduction of anion radical, and addition of anion radical to the cation radical. This concept has been nicely demonstrated by Gassman et al. [103, 104], using the photoinduced electron-transfer cydization of y,8-unsatu-rated carboxylic add 232 to y-ladones 233 and 234 as an example (see Scheme 8.65). 

Both nucleophilic and electrophilic reactions are known, and the reaction sequence can be directed by a suitable choice for a heteroligand [41,52], As suggested by Scheme 6.11a, the ability of the heteroligand to direct electrophilic or nucleophilic attack by the peroxocomplex can provide an important tool in oxidative reactions, where selectivity of action is required. A second mode of electrophilic reaction chemistry is available through attack of sulfur electrons at the vanadium center to give a transient anion/cation radical pair via formation of V(TV) and S-+ (Scheme 6.1 lb). 

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