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Herein, an efficient strategy for accessing highly functionalized borylated 9- to 11-membered lactams is established, relying on photocatalytic cascade ring expansion of unstrained cyclic amines with N-heterocyclic carbene (NHC)-borane. Notably, this methodology features mild conditions, excellent functional group tolerance, and great downstream transformations, providing a powerful and practical platform for constructing diverse medium-ring lactams. Mechanistic studies support a radical mechanism involving nucleophilic NHC-boryl radical formation, radical ipso-cyclization, and subsequent 1,4-aryl migration from N-to-C atom to release the desired ring-expanded lactams.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03348","type":"journal-article","created":{"date-parts":[[2026,9,5]],"date-time":"2026-09-05T02:02:03Z","timestamp":1788573723000},"page":"11707-11712","source":"Crossref","is-referenced-by-count":0,"title":["Photocatalytic\nSynthesis of Medium-Sized Lactams via\nCascade Ring Expansion Reaction of Unstrained Cyclic Amines with NHC-Borane"],"prefix":"10.1021","volume":"28","author":[{"given":"Dan-Na","family":"Chen","sequence":"first","affiliation":[{"name":"Guangxi Normal University , , ,","place":["Guilin, P. R. China, 541004"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fu-Qin","family":"Zhang","sequence":"additional","affiliation":[{"name":"Guangxi Normal University , , ,","place":["Guilin, P. R. 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