Abstract

The hypervalent‐iodine‐mediated oxidative metal‐free cross‐coupling reaction of thiophenes with various pyrroles was developed. The corresponding thiophene–pyrrole derivatives were obtained in moderate to high yields (up to 85 %). This method features high efficiency and regioselectivity and broad functional group tolerance. We further determined the highly planar characteristics of the 3,4‐ethylenedioxythiophene–pyrrole biaryls caused by intramolecular hydrogen bonding.

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