Abstract

Here we report a metal‐ and light‐free decarboxylative functionalization approach enabled by reduced nicotinamide adenine dinucleotide (NADH) analogues. The efficient and operationally simple approach, conducted in 5 minutes from in‐situ preparation of aryliodine (III) dicarboxylates under open‐air and ambient conditions, enables diverse bond formation and exhibits a broad substrate scope of over 70 examples. Late‐stage functionalization of drug molecules and natural products further demonstrates the synthetic utility of this method. Combined experimental and computational studies elucidate the mechanistic pathway. These transformations streamline the synthesis of sp3 carbon‐enriched compounds, adding a new dimension to classical decarboxylative reactions.

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