Living Anionic Addition Reaction of 1,1-Diphenylethylene Derivatives: One-Pot Synthesis of ABC-type Chain-End Sequence-Controlled Polymers.
J Am Chem Soc
; 143(30): 11296-11301, 2021 08 04.
Article
en En
| MEDLINE
| ID: mdl-34232655
ABSTRACT
In this study, a 11 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 ß-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.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Asunto principal:
Poliestirenos
/
Estirenos
Idioma:
En
Revista:
J Am Chem Soc
Año:
2021
Tipo del documento:
Article
País de afiliación:
Japón