Synthesis of Phenanthrenes and 1-Hydroxyphenanthrenes via Aromatization-Assisted Ring-Closing Metathesis: toward Polynuclear Aromatic Hydrocarbons.

This study presents an efficient synthetic strategy for phenanthrenes and 1-hydroxyphenanthrenes through aromatization-assisted ring-closing metathesis (RCM). It involves vinylation of 1-bromo-2-naphthaldehyde derivatives, Barbier allylation, and subsequent one-pot RCM/dehydration of the diene precursors to yield phenanthrene derivatives. Further, the corresponding keto analogues of diene precursors produce 1-hydroxyphenanthrenes through RCM and aromatization-driven keto-enol tautomerism. This pathway enables rapid access to a diverse array of functionalized phenanthrenes and 1-hydroxyphenanthrenes, including synthetically challenging derivatives containing both -OH and -OMe groups via the sequential construction of the terminal phenanthrene ring.