Anion‐(π)n‐π Catalytic Micelles

Anion‐π catalysis operates by stabilizing anionic transition states on π‐acidic aromatic surfaces. In anion‐(π)n‐π catalysis, π stacks add polarizability to strengthen interactions. In search of synthetic methods to extend π stacks beyond the limits of foldamers, the self‐assembly of micelles from amphiphilic naphthalenediimides (NDIs) is introduced. To interface substrates and catalysts, charge‐transfer complexes with dialkoxynaphthalenes (DANs), a classic in supramolecular chemistry, are installed. In π‐stacked micelles, the rates of bioinspired ether cyclizations exceed rates on monomers in organic solvents by far. This is particularly impressive considering that anion‐π catalysis in water has been elusive so far. Increasing rates with increasing π acidity of the micelles evince operational anion‐(π)n‐π catalysis. At maximal π acidity, autocatalytic behavior emerges. Dependence on position and order in confined micellar space promises access to emergent properties. Anion‐(π)n‐π catalytic micelles in water thus expand supramolecular systems catalysis accessible with anion‐π interactions with an inspiring topic of general interest and great perspectives. Anion‐(π)n‐π catalytic micelles are introduced to expand the collection of systems catalysts compatible with anion‐π catalysis with a rich topic of general importance. They are of interest to realize anion‐π catalysis, anion‐(π)n‐π catalysis and anion‐(π)n‐π autocatalysis in water. Classics in supramolecular chemistry are installed to control substrate binding and positioning within the confined micellar space for access to emergent properties.