Step-wise and one-pot synthesis of highly substituted conjugated trienes from 2-oxobenzo[h]chromenes/2H-pyran-2-ones

Abstract

A mild and efficient route for the synthesis of conjugated trienes via nitroethane-mediated ring contraction of 2-oxobenzo[h]chromenes/2H-pyran-2-ones followed by decarboxylative rearrangement of the obtained spirobutenolides and butenolides is described. The (E)-isomer of trienes was obtained by step-wise and one-pot approaches from 2-oxobenzo[h]chromenes. Butenolides 4a–l as new substrates have been developed for the construction of trienes. The mixture of the (E)- and (Z)-isomers of spirobutenolides undergoes decarboxylative rearrangement in the presence of sodium ethoxide as a base to yield the (E)-isomer of trienes, while the (E)-isomer of butenolides reacts to give a mixture of (2E,4E)- and (2E,4Z)-isomers of trienes in an almost steady ratio of 45 : 55 or 1 : 1.2. The structure and geometry of the obtained butenolides and trienes were confirmed by single-crystal X-ray analysis.