Total synthesis of streptovertidione and bioinspired transformation to streptovertidine A and formicapyridine A.

We report herein a concise total synthesis of streptovertidione, and its transformation to streptovertidine A and formicapyridine A through a bioinspired pyridination. This strategy features: (1) a one-pot Ti(O- i Pr) 4 -mediated photoenolization/Diels-Alder (PEDA) reaction/oxidative aromatization sequence for the construction of gem -dimethyl-anthracenone, a naturally occurring antibiotic pharmacophore; (2) a late-stage pyridination based on the biosynthetic hypothesis. This efficient route supports the preparation of other formicapyridines and derivatives.