TpRuPPh(3)(CH(3)CN)(2)PF(6) catalyzed the transformation of various 3-benzyl but-1-ynyl ethers into dienes and benzaldehyde at a catalyst loading of 5 mol %. This process represents an atypical pattern of transfer hydrogenation. This catalytic reaction can be applied to various derivatives of 2-ethynyl tetrahydrofurans and pyrans to cleave their ether rings and gives diene and tethered aldehyde functionalities, respectively.