Divergent Transformations of 2‑Nitro‑1H‑benzo[f]chromenes in Reactions with Alkylidenemalononitriles: Access to Naphtho[2,1‑b]furans via Base-Mediated Pyran Ring Contraction

The action of 2-(1-arylethylidene)malononitriles on 2-nitro-1H-benzo[f]chromenes in the presence of Et₃N and MoO₃·2H₂O results in naphtho[2,1-b]furans containing an allylidenemalononitrile unit in the α-position. The reaction proceeds with contraction of the pyran ring via a cascade carba-Michael addition/retro-oxa-Michael reaction/tautomerization/S_N2/oxidation process. In contrast, the reaction of 2-nitro-1H-benzo[f]chromenes with the cyclic Knoevenagel adduct derived from 1-indanone and malononitrile leads to dihydroindeno[1,2-c]xanthenes. The possibility of further transformations of naphtho[2,1-b]furan derivatives as useful precursors and their optical properties were also investigated.