A Step-Efficient Pathway to Chlorine-Functionalized Thiophene Oligomers by Palladium-Catalyzed Deprotonative Coupling of Chlorothiophenes

Dedicated to Professor Tamejiro Hiyama on the occasion of his 70^th birthday

Abstract

Deprotonative metalation of 2-chloro-3-substituted thiophene at the 5-position of the thiophene ring is performed by using a bulky magnesium amide 2,2,6,6-tetramethylpiperidin-1-yl magnesium chloride lithium chloride salt (TMPMgCl·LiCl). The obtained metallic species reacts with bromothiophene to afford the regioregular head-to-tail-type chlorobithiophene, which is subjected to further end functionalization by the coupling reaction with the C–Cl bond. Deprotonative C–H coupling polycondensation of substituted chlorobithiophene derivatives gives polythiophene as a formal alternating copolymer.

Key words

thiophene oligomer - palladium catalyst - chlorothiophene - Knochel–Hauser base - alternating copolymer

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