Here, by re-examining our stereoselective synthesis of MAC rotaxanes, we identify that a single H-bond between the sulfoxide unit and one of the two half-axle components plays a key role in the reaction outcome. We use this understanding to develop a stereoselective approach to rotaxane MGI-1 isomers, which can be extended directly to their catenane counterparts. Finally, we apply our understanding to the direct synthesis of MAC rotaxanes without the need to produce diastereomeric intermediates.