Tandem Claisem Rearrangement: Synthesis of Novel FunctionalPhenol Derivatives

摘要

The reaction of 3-chloro-2-chloromethyl-1-propene with 2 equimolar phenolic compounds gave isobutenyl bis(aryl) ether compounds. The thermal or Lewis acid-assisted Claisen rear-rangement of the ether compounds results in generating pheolic compounds having plural hydroxyl groups at one step reaction. We named this reaction as "tandem Claisen rearrangement," here the Claisen rearrangement sucessively occurs two times at each isobutenyl ether moiety. This reaction can be applied not only to acyclic, but also to macrocyclic compounds having isobutenyl ether moiety. Tetradentate ligands with two quinolinol moieties, tripodal hexadentate ligands with either three quinolinol or catechol moieties, etc. have been synthesized as acyclic rearraged products. As macrocyclic rearranged products, various kinds of novel crownophane and cyclophane derivatives having plural hydroxyl groups have been synthesized. These compounds prepared via tandem Claisen rearrangement have been found to be able to work as ionophore, fluorophoire, host molecules for neutral organic molecules, chiral ones, ligands for transition metal ions and so on.