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In bicyclic structures, endo and exo refer to the relative positions of substituents on a bridgehead carbon (a carbon atom shared by two rings). Endo describes a substituent that lies on the same side of the bridge as the larger ring, while exo describes a substituent that lies on the opposite side of the bridge as the larger ring. The endo and exo designations are used to distinguish between different stereoisomers of bicyclic compounds, impacting their physical and chemical properties.