Radical polymerization of styrene derivatives having a series of amino acid, alanine, glycine, leucine, valine, Bocleucine, and Boc-valine, in the side chain bound at the C-terminal was conducted to regulate the stereoinduction system in the propagation step. Isotacticity increased in the polymer main chain, especially in the polymerization of monomers bearing N-free L-leucyl and L-valyl esters in THF or DMF at 50 degrees C, by the synergic stereoregulation with chirality control and hydrogen bonding between the radical polymer terminal and the monomer. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5593-5602, 2010

Novel styrene monomer bearing alanyl ester with or without free amino terminus was synthesized and polymerized with AIBN at80°C via radical pathway.A Boc-protected4’vinylbenzyl-alanyl ester was synthesized by a reaction of4’-vinylbenzyl chloride with Bocalanine in the presence of triethylamine and ethanol at80°C.This condition is similar to one of a synthetic method introducing N-Boc-protected peptides to the polystyrene resin in the Merrifield technique.However,this coupling reaction led to the formation of some byproducts,and alternatively,treatment of them with an inorganic base at60°C in DMF solution containing small amount of water afforded successful formation of the N-Boc-protected alanyl ester in good yield.Deprotection of the Boc-group from the ester gave the monomer with free amino moiety.The styrene derivatives were polymerized with AIBN at80°C to yield polystyrenes with high molecular-weight. Department of Chemistry,Faculty of Science,Fukuoka University,Nanakuma,Jonan-ku,Fukuoka814‐0180, Japan 福岡大学理学集報 35(2)25~31(2005) -25-