1. Living Anionic Addition Reaction of 1,1-Diphenylethylene Derivatives: One-Pot Synthesis of ABC-type Chain-End Sequence-Controlled Polymers
- Author
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Satoshi Uchida, Kazuki Takahata, Raita Goseki, Masashi Nagao, Naoki Aizawa, and Takashi Ishizone
- Subjects
Anions ,chemistry.chemical_classification ,Addition reaction ,Molecular Structure ,Double bond ,Trimethylsilyl ,Chemical shift ,One-pot synthesis ,General Chemistry ,Biochemistry ,Medicinal chemistry ,Catalysis ,Polymerization ,Styrenes ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,chemistry ,Electrophile ,Polystyrenes ,Polystyrene ,Stoichiometry - Abstract
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.
- Published
- 2021