The sequence of bifurcations leading to the onset of chaotic flow is determined numerically, for the case of a buoyant plume arising from a horizontal cylinder, centred in a square-sectioned, air-filled enclosure. In the frame of the 2D assumption, a specifically-developed high resolution simulation procedure is adopted, with the aim of achieving a detailed description of the transitional dynamics occurring within the system. A large number of simulations are performed, allowing for an accurate estimate of the critical values of the main system parameter, the Rayleigh number Ra, at which bifurcations occur. A single value of the geometric aspect ratio A of the system is considered, for which transition is found to be characterized by an imperfect period-doubling cascade, an uncommon behaviour in thermofluid systems. Peculiarities of the route to chaos are highlighted, such as the existence of a window of quasiperiodic flow, and the detection of high-order period orbits.