A Unified Strategy for the Total Synthesis of the Angucycline Antibiotics SF 2315A, Urdamycinone B, and the Shunt Metabolite 104–2

Total syntheses of the angucycline antibiotics SF 2315A ( 2 ), urdamycinone B ( 4 ), and the shunt metabolite 104–2 ( 5 ) are described, as well as an approach toward the synthesis of SF 2315B ( 3 ). All four syntheses feature a Diels–Alder cycloaddition between a bromojuglone derivative and an optically active diene ( 25a ), the latter derived from (–)‐quinic acid. Subsequent key transformations include (i) stereocontrolled introduction of ring fusion oxygen functionality featured in SF 2315A ( 2 ) and SF 2315 B ( 3 ), (ii) preparation of C‐glycosyl juglone 53 , and (iii) NMO mediated oxidative aromatization of 60.