The singular reduction of 1,8-bis-hydroxymethylnaphthalene to a benzonorcaradiene by LiAlH4

Article abstract of DOI:10.1016/S0040-4039(97)10247-7

Reduction of 1,8-naphthalic anhydride (1) with LiAlH₄ in THF (or DME, but not Et₂O) affords, in addition to diol 2, benzonorcaradiene 3. Extended treatment of 2 or lactone 4 also leads to 3, in 66% and 65% yield, respectively. Reduction of 4 with LiAlD₄ established that formation of 3 proceeds via a symmetrical intermediate. No significant norcaradiene formation is observed upon comparable LiAlH₄ treatment of 14,15,16 or 17. This novel reduction of a naphthalene derivative to a benzonorcaradiene appears to be unique to 2 or its precursors.