The unusual bond reorganization of 1,3-diynes to 1,5-dien-3-ynes mediated by metal carbene species has been reported under transition metal-catalyzed conditions. Considering the frequent presence of this multiply conjugated unsaturated system in many biologically active natural products such as enediynes as well as in non-natural scaffolds possessing important optical and electrical properties like in polydiacetylenes, the efficient method for the synthesis of this functionality should warrant further development. To broaden the scope of this novel and potentially powerful bond reorganization process, the capacity of carbophilic transition metals to generate metal carbene intermediate directly from appropriate alkynes has been envisioned to carry out the expected bond reorganization process. In this presentation, an efficient rearrangement of 1,3-diynes possessing propargylic heteroatom substituents to functionalized 1,5-dien-3-ynes (eq 1) in the presence of transition metal catalysts will be described.