Construction of Complex Bisether-Bridged Medium-Sized Cyclic Compounds from o‑(1-(Acyloxy)propargyl)benzaldehydes under Base and Acid Catalysis

We report herein our serendipitous discovery of the rapid and straightforward accesses to unprecedented diverse complex molecular structures from readily available starting materials. Catalyzed by 1,8-diazabicyclo[5.4.0]­undec-7-ene under mild conditions, o-(1-(acyloxy)­propargyl)­benzaldehydes 1 underwent efficient and selective dimerization reactions to produce novel complex bisether-bridged tricyclic products 3 and 4. The reactions proceeded most probably through dimerizations between 3-methylene-3H-isochromene intermediate and its zwitterionic resonance structures which were generated from a concerted 6-π electrocyclic ring closure reaction from the initially formed (2-formylphenyl)­allene intermediates derived directly from o-(1-(acyloxy)­propargyl)­benzaldehydes. Treatment of the resulting product simply with NaOEt in ethanol and aqueous HCl, respectively, enabled further development of complex molecular diversities.