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/SN2/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.

Catalyst-free formal [3 + 2] cycloaddition of stabilized N,N-cyclic azomethine imines to 3-nitrobenzofurans and 3-nitro-4H-chromenes: access to heteroannulated pyrazolo[1,2-a]pyrazoles.

We have studied the [3 + 2]-cycloaddition of various N,N-cyclic azomethine imines to 3-nitrobenzofurans. This process is a rare example of their dearomatization. We have also extended this process to the related 3-nitro-4H-chromenes as dipolarophiles. Both reactions provide access to benzofuro- and chromeno-condensed pyrazolo[1,2-a]pyrazoles with 100% atom economy in a diastereoselective manner under mild eco-friendly conditions. Finally, on the basis of DFT calculations, the mechanistic insights into the mentioned [3 + 2]-cycloadditions and explanations of the experimentally determined limitations of the method are given. Hirshfeld atomic charge values of push-pull heterocycles were suggested as a criterion for a priori assessment of the possibility of their dipolar cycloaddition with N,N-cyclic azomethine imines.