50% to ca. 95% when comparing the new nanohoop organocatalyst with structurally comparable, simple BINOL phosphoric acids. While the scope for 2-aryl substituted quinolines was wide and surprisingly even included sterically rather demanding substrates, we found that 2-alkyl quinolines were not good substrates for our catalyst, which is in stark contrast to simpler catalysts that are highly effective for this type of substrates. Diverse studies on this unexpected finding point towards a highly specific effect that is due to the exceptionally strong binding of alkyl substrates to the macrocycle in conjunction with the lack of turnover. We expect that this work will inspire researchers with an interest in shape-persistent macrocycles to test compounds that are relatively easy to synthesize as catalysts. Likewise, researchers with an interest in organocatalysis may be well-advised to tackle their hardest problems with catalysts that are rigid, yet topologically non-trivial (e.g. macrocyclic, bowl-shape, cage-like, 69,70 mechanically interlocked 71 ).