The early stages of the spontaneous hydrolytic polymerization of an active hydroxide in the anti-bayerite structure are followed by using molecular dynamics simulations. The polymer populations are calculated as a function of reaction progress and compared with a model governed by purely random bonding. In agreement with experimental observations in aqueous solutions. the transformation of singly bridged to doubly bridged metal ions is shown to have a significant autocatalytic component. The overall polymer populations, however, are very close to the predictions of the random bonding model, indicating that local autocatalytic behavior is decoupled from multimer populations at the larger scales. The calculations show that solid-state transformation processes do not preferentially give rise to higher order multimers, and suggest that interfacial processes, involving bulk solution, are required to facilitate rapid transformation to higher order oligomers. Two reaction pathways are identified for the dewatering of mu H3O2 bridges into mu-OH bridges. Both are activated primarily by undercoordination of one of the metals centers involved in the bridge.