Abstract The palladium‐catalyzed tail‐to‐tail reductive dimerization of terminal alkynes is described for the first time. Aromatic terminal alkynes bearing diverse and sensitive functional groups as well as aliphatic terminal alkynes are efficiently transformed to 2,3‐dibranched butadienes. The key to achieve a selective tail‐to‐tail reductive dimerization reaction is to control appropriately the acidity of the reaction solution, which is accomplished by a combined use of pivalic acid and para‐toluenesulfonic acid. The tail‐to‐tail reductive dimerization reaction is proposed to proceed via a cationic alkenyl palladium intermediate under acidic conditions.
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