4. Lewis Acids in Radical-Based Polymer Synthesis

The first attempts to control stereochemistry in radical polymerization by the use of LAs were reported over 50 years ago. In the early 1960s, Bovey examined the effect of catalytic amounts of zinc chloride (ZnCl2) on the radical polymerization of MMA, noting no significant stereochemical effects.139 Otsu et al. later found that stoichiometric amounts of ZnCl2 slightly increased the isotacticity of the resulting poly(MMA).140 Given these initially underwhelming results, LA-mediated radical polymerization remained relatively unexplored, with few investigations reported in the 1970s and 1980s. However, following the successful application of LAs in small-molecule radical transformations throughout ...

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