One-Pot Synthesis of an ABCD-type Multifunctionalized Chain-End Sequence-Controlled Polymer through “Living Anionic Addition Reaction” Using 1,1-Diphenylethylene Derivatives Containing Functional Groups

A repeating 1:1 addition reaction using 1,1-diphenylethylene (DPE) derivatives, known as “living anionic addition reaction (LAAR),” was performed to construct defect-free DPE sequences composed of nonhomopolymerizable vinyl compounds at the polystyrene terminals. In addition to the parent nonsubstituted DPE, five functional DPE derivatives possessing electron-donating (N,N-dimethylamino and trialkylsilyloxy) and electron-withdrawing (bromo, acyl, and cyano) groups were employed in the LAAR using a living difunctional polystyryl anion. The relative reactivity of the derivatives was predicted by their Hammett substituent constant σp and vinyl β-carbon chemical shifts. The stoichiometric addition reaction between the resulting DPE anion and more electrophilic DPE derivatives quantitatively proceeded in one direction, even in the presence of residual less reactive derivatives. The sequential addition of DPE derivatives in increasing order of their relative electrophilicity to living anionic polystyrene successfully generated 13 AB-, 11 ABC-, and one ABCD-type chain-end sequence-controlled polystyrenes with well-defined structures in one-pot reactions.