Recent advances in molecular dynamics simulations of rare reaction events and aggregation processes are reviewed. Therein the central focus is dedicated to employing the transition path sampling method to study reactions in solution. We describe systematic approaches for generating initial transition pathways and efficient strategies for computationally feasible exploration of further transition routes. The unprejudiced study of reaction mechanisms is illustrated for reactions in aqueous solution and other complex systems. Transition path sampling allows very detailed investigation of solvent effects. Apart from stabilization of reactant, transition, or product state ensembles, this also includes the role of the solvent as a heat bath and as a putative reaction partner. The latter issue is of particular importance for reactions in aqueous solutions, which involve proton-transfer steps that may be assisted by water molecules via the Grotthuss mechanism.