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At ransitionm etal-free,f acile and efficient one-pot protocol for the synthesiso fp ropynenitriles from readilya vailable 3-chloropropenals is disclosed. Ther eactionc onditions have also been optimized for the exclusive formation and isolation of 3-chloropropenenitriles which are important building blocks in general anda re intermediates in the synthesis of propynenitriles.T he hallmark of the methodology is the use of non-toxic reagents, milder, metal-free ande conomically benign reaction conditions avoiding ah arsh dehydration step while achieving excellent yields.