Hybrid simulation procedures which combine molecular dynamics with Monte Carlo are attracting increasing attention as tools for improving the sampling efficiency in molecular simulations. In particular, encouraging results have been reported for nonequilibrium candidate protocols, in which a Monte Carlo move is applied gradually, and interleaved with a process that equilibrates the remaining degrees of freedom. Although initial studies have uncovered a substantial potential of the method, its practical applicability for sampling structural transitions in macromolecules remains incompletely understood. Here, we address this issue by systematically investigating the efficiency of the nonequilibrium candidate Monte Carlo on the sampling of rotameric distributions of two peptide systems at atomistic resolution both in vacuum and explicit solvent. The studied systems allow us to directly probe the efficiency with which a single or a few slow degrees of freedom can be driven between well-separated free energy minima and to explore the sensitivity of the method toward the involved free parameters. In line with results on other systems, our study suggests that order-of-magnitude gains can be obtained in certain scenarios but also identifies challenges that arise when applying the procedure in explicit solvent.