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The addition of individual quanta of rotational excitation to a molecule has been shown to markedly change its reactivity by significantly modifying the intermolecular interactions. So far, it has only been possible to observe these rotational effects in a very limited number of systems due to lack of rotational selectivity in chemical reaction experiments. The recent development of rotationally controlled molecular beams now makes such investigations possible for a wide range of systems. This is particularly crucial in order to understand the chemistry occurring in the interstellar medium, such as exploring the formation of carbon-based astrochemical molecules and the emergence of molecular complexity in interstellar space from the reaction of small atomic and molecular fragments.