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Generation of Sodium-Thiophene Species with Metal Amide-Free Approach Toward Polythiophene Synthesis by Cross-Coupling Polymerization
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Generation of Sodium-Thiophene Species with Metal Amide-Free Approach Toward Polythiophene Synthesis by Cross-Coupling Polymerization

Tomoki Inoue, Aika Kuwayama, Kentaro Okano, Masaki HorieAtsunori Mori
Asian Journal of Organic Chemistry
2022

摘要

Chlorothiophene Nickel catalyst Phenyl sodium Polythiophene TMEDA Organic Chemistry
Deprotonative metalation of 2-halo-3-substituted thiophene in a metal amide-free manner takes place at the 5-position smoothly in the presence of additive N,N,N′,N′-tetramethylethylenediamine (TMEDA) at room temperature in a hexane solution. Following addition of nickel catalyst to the thus formed thiophene-sodium species promotes cross-coupling polymerization. When toluene was employed as a solvent in the polymerization reaction of 2-chloro-3-hexylthiophene in the presence of 2 mol% of nickel catalyst bearing N-heterocyclic carbene ligand, polythiophene was obtained in up to 86% yield with M n of 23700 (M w /M n =1.98) suggesting that ca. 30% of the catalyst participated in the polymerization.

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