Pintu Kumbhakar, Mrinmay Baidya, Sourav Pal, Suman De Sarkar
We report an electrochemical strategy for the diastereoselective formylation of enamines via the anodic decarboxylation of glyoxylic acid. This sustainable, metal- and chemical-oxidant-free protocol enables efficient C–C bond formation under mild conditions, affording formylated products in yields of up to 87% across 32 examples with good diastereoselectivity. Furthermore, an electrolyte-free variant was developed that demonstrated broad applicability to diverse substrates, highlighting the practical robustness of the approach. Mechanistic investigations combining electrochemical analysis and control experiments indicate a sequence of ionic and radical events that drive product formation. This work underscores the potential of electrochemical strategies to enable selective and sustainable C–C bond construction.