zur Bonsen, A.B.Sumby, C.J.George, J.H.2023-08-302023-08-302023Organic Letters, 2023; 25(34):6317-63211523-70601523-7052https://hdl.handle.net/2440/139346Published: August 22, 2023Hyperireflexolides A and B were synthesized in six steps via the dearomatization and fragmentation of a simple acylphloroglucinol starting material. The dearomatized acylphloroglucinol undergoes a sequence of oxidative radical cyclization, retro-Dieckmann fragmentation, stereodivergent intramolecular carbonyl-ene reactions, and final α-hydroxy-β-diketone rearrangements to give the target natural products. This sequence is based on a biosynthetic proposal that claims the hyperireflexolides as highly rearranged polycyclic polyprenylated acylphloroglucinols (PPAPs), which is supported by the structural revision of hyperireflexolide B.en© 2023 American Chemical SocietyChemical synthesis; Fragmentation; Organic synthesis; Pharmaceuticals; RearrangementJournal article10.1021/acs.orglett.3c022322023-08-30654447zur Bonsen, A.B. [0000-0001-9111-3876]Sumby, C.J. [0000-0002-9713-9599]George, J.H. [0000-0002-7330-2160]