ポリマー固定化エコ反応剤の開発 : 生理活性分子，高機能性分子の次世代合成ストラテジー

Chalcones with the 2’-benzoyloxy group can be transformed into the corresponding isoflavones by action
of polymer-supported IBD (PSIBD, poly[4-(diacetoxy)iodo]styrene) with TsOH. The advantage of the reaction
is no liberation of PhI and reuse of the reagent. Meanwhile, fulleropyrrolidines have been very welcomed in a
community of a fullerene science. But sometimes the synthesis ends up with disappointing yields of the
products. We found that the dipolar cycloaddition of an azomethine ylide, i.e., 2-phenyl-N-benzylideneglycine
methyl ester, supported on a Wang resin, proceeded feasibly with C60 and the objective fulleropyrrolidines were
afforded in good yields (>75%). The method is expected to be utilized with wide range of application and it is
therefore able to provide a compound library of modified fullerenes which is hard to be obtained by other
methods employed so far.
In order to introduce carboxyl groups into a thermoresponsive dehydroalanine polymers and
hydrogels, N-isobutyryldehydroalanine methyl ester (iBDHAM) were copolymerized with its carboxylic
acid derivative (iBDHA) for linear polymers and with a bisdehydroalanine derivative,
N,N’-succinylbisdehydroalanine (SBDHA) for hydrogels. The linear copolymer, P(iBDHA-co-iBDHAM)
([iBDHA]=23-81%), showed LCST behavior in deionized water, but the LCST values were highly
polymer concentration-dependent. It is concluded that effect of carboxyl groups introduced into the
polymer chain is larger in hydrogels than in linear polymer. This is probably due to the effect of
dissociative carboxyl groups on the osmotic pressure of hydrogels.