We investigate the loss of chaos synchronization in coupled chaotic systems without symmetry from the point of view of bifurcations of unstable periodic orbits embedded in the synchronous chaotic attractor (SCA). A mechanism for direct transition to global riddling through a transcritical contact bifurcation between a periodic saddle embedded in the SCA and a repeller on the boundary of its basin of attraction is thus found. Note that this bifurcation mechanism is different from that in coupled chaotic systems with symmetry. After such a riddling transition, the basin becomes globally riddled with a dense set of repelling tongues leading to divergent orbits. This riddled basin is also characterized by divergence and uncertainty exponents, and thus typical power-law scaling is found.