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Herein, we report two imidazolium\u2010functionalized cationic covalent organic cages featuring distinct cavity architectures, including a triangular\u2010prismatic cavity (\n                    <jats:bold>cage 1<\/jats:bold>\n                    ) and a bowl\u2010shaped cavity (\n                    <jats:bold>cage 2<\/jats:bold>\n                    ), as confined platforms for oxidant\u2010free Hofmann\u2013L\u00f6ffler\u2013Freytag (HLF)\/cyclization cascade catalysis. Both cages efficiently mediate a one\u2010pot transformation of\n                    <jats:italic>N<\/jats:italic>\n                    \u2010chloroamides into pyrrolidine derivatives under mild conditions, whereas\n                    <jats:bold>cage 1<\/jats:bold>\n                    exhibits substantially enhanced activity and selectivity relative to\n                    <jats:bold>cage 2<\/jats:bold>\n                    and a monomeric analog. Mechanistic investigations suggest that the geometrically confined cationic cavity of\n                    <jats:bold>cage 1<\/jats:bold>\n                    promotes substrate preorganization through cooperative host\u2013guest interactions, stabilizes nitrogen\u2010centered radical intermediates via electrostatic and C\u2013H\u00b7\u00b7\u00b7\u03c0 interactions, and facilitates the key 1,5\u2010hydrogen atom transfer (1,5\u2010HAT) process by lowering the associated activation barrier. Host\u2013guest binding studies and DFT calculations, reveal a structure\u2013recognition\u2013reactivity relationship in which substrate anchoring, spin delocalization, and cavity confinement collectively govern catalytic efficiency. These findings demonstrate how confined cationic microenvironments can reconstruct radical cascade pathways and provide a general strategy for designing supramolecular catalysts for selective multistep transformations.\n                  <\/jats:p>","DOI":"10.1002\/anie.2488797","type":"journal-article","created":{"date-parts":[[2026,6,30]],"date-time":"2026-06-30T08:07:28Z","timestamp":1782806848000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Confined Cationic Covalent Organic Cages Enable Oxidant\u2010Free Hofmann\u2212L\u00f6ffler\u2212Freytag\/Cyclization Sequences"],"prefix":"10.1002","volume":"65","author":[{"given":"Cheng","family":"Wang","sequence":"first","affiliation":[{"name":"International Joint Laboratory on Resource Chemistry of the Ministry of Education Shanghai Engineering Research Center of Green Energy Chemical Engineering Shanghai Normal University  Shanghai People's Republic of 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