Radical mediators

Most polymerizations in this section can be categorized as stable (Tree) radical-mediated polymerizations (sometimes abbreviated as SFRMP). In the following discussion systems have been classed according to the type of stable radical involved, which usually correlates with the type of bond homolyzed in the activation process. Those described include systems where the stable radical is a sulfur-ccntered radical (Section 9.3.2), a selenium-centered radical (Section 9.3.3), a carbon-centered radical (Sections 9.3.4 and 9.3.5), an oxygen-centered radical (Sections 9.3.6, 9.3.7), or a nitrogcn-ccntcrcd radical (Section 9.3.8). Wc also consider polymerization mediated by cobalt complexes (Section 9.3.9) and certain monomers (Section 9.3.5). 

Stable carbon-centered radicals, in particular, substituted diphenylmethyl and triphenylmethyl radicals, couple reversibly with propagating radicals (Scheme 9.11). With, the carbon-centered radical-mediated polymerization systems described to dale, the propagating radical should be tertiary (e.g. methacrylate ester) to give reasonable rates of activation. 

Other Oxygen-Centered Radical-Mediated Polymerizations... 

Metal complexes may also act as initiators in stable radical-mediated polymerization with the metal complex performing the role of the stable radical. 

SFRMP stable free radical mediated polymerization... 

ORl OX w di-Miutyl peroxyoxalalc deactivation by reversible chain transfer and bioinolecular aclivaiion 456 atom transfer radical polymerization 7, 250, 456,457, 458,461.486-98 deactivation by reversible coupling and untmolecular activation 455-6, 457-86 carbon-centered radical-mediated poly nierizaiion 467-70 initiators, inferlers and iriiters 457-8 metal complex-mediated radical polymerization 484... 

Radical-mediated silyldesulfonylation of various vinyl and (a-fluoro)vinyl sulfones 21 with (TMSlsSiH (Reaction 25) provide access to vinyl and (a-fluoro)vinyl silanes 22. These reactions presumably occur via a radical addition of (TMSlsSi radical followed by /)-scission with the ejection of PhS02 radical. Hydrogen abstraction from (TMSlsSiH by PhS02 radical completes the cycle of these chain reactions. Such silyldesulfonylation provides a flexible alternative to the hydrosilylation of alkynes with (TMSlsSiH (see below). On oxidative treatment with hydrogen peroxide in basic aqueous solution, compound 22 undergoes Pd-catalyzed cross-couplings with aryl halides. 

Kim and coworkers introduced silyl radical mediated addition of alkyl radical to silyloxy enamine 76. The silyloxy enamine moiety is readily accessible from a variety of functionalities. The mechanistic concept is illustrated in the Scheme 12 and involves the addition of R radical to 76 to give the radical adduct 77 and the subsequent homolytic cleavage of N-O bond to yield the desired product 78 and a silyloxy radical 79. The latter undergoes 1,2-phenyl migration to give the silyl radical 80 that abstracts halogen from the alkyl halide to regenerate the R radical. 

Unsaturated azocinones were synthesized by 2 -i- 2 cycloaddition of benzoni-triles to phenols and a final radical mediated fragmentation [67]. 

Diabetic patients have reduced antioxidant defences and suffer from an increased risk of free radical-mediated diseases such as coronary heart disease. EC has a pronounced insulin-like effect on erythrocyte membrane-bound acetylcholinesterase in type II diabetic patients (Rizvi and Zaid, 2001). Tea polyphenols were shown to possess anti-diabetic activity and to be effective both in the prevention and treatment of diabetes (Choi et al, 1998 Yang et al, 1999). The main mechanism by which tea polyphenols appear to lower serum glucose levels is via the inhibition of the activity of the starch digesting enzyme, amylase. Tea inhibits both salivary and intestinal amylase, so that starch is broken down more slowly and the rise in serum glucose is thus reduced. In addition, tea may affect the intestinal absorption of glucose. 

KERRY N and ABBEY M (1998) The isoflavone genistein inhibits copper and peroxyl radical mediated low density lipoprotein oxidation in vitro. Atherosclerosis. 140 (2) 341-7. 

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