Living Anionic Addition Reaction of 1,1-Diphenylethylene Derivatives: One-Pot Synthesis of ABC-type Chain-End Sequence-Controlled Polymers

• Published in: Journal of the American Chemical Society Vol. 143; no. 30; pp. 11296 - 11301
• Main Authors: Takahata, Kazuki, Aizawa, Naoki, Nagao, Masashi, Uchida, Satoshi, Goseki, Raita, Ishizone, Takashi
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04.08.2021
• Subjects: Anions - chemistry; Molecular Structure; Polymerization; Polystyrenes - chemical synthesis; Polystyrenes - chemistry; Styrenes - chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.1c04500

In this study, a 1:1 addition reaction using 1,1-diphenylethylene (DPE) derivatives, referred to as the “living anionic addition reaction”, was established to regulate the sequence of vinyl compounds having negligible homopolymerizability. The stoichiometric and successive addition reaction between a DPE anion and more reactive DPE derivatives proceeded quantitatively when the electrophilicity of the DPE derivatives was sufficiently enhanced by electron-withdrawing groups such as (trimethylsilyl)­ethynyl and acyl groups. The relative electrophilicity of the DPE derivatives was predicted by Hammett’s law and the β-carbon chemical shifts of the carbon–carbon double bonds. AB- and ABC-type chain-end sequence-controlled polystyrenes with well-defined structures were synthesized by reacting two or three DPE derivatives with difunctional anionic living polystyrene in increasing order of their electrophilicity in a one-pot reaction.