Synthesis of an Ellagitannin Component, the Macaranoyl Group with a Tetra- ortho -Substituted Diaryl Ether Structure.

Herein, a practical synthesis of the macaranoyl group contained in ellagitannins, i.e., a C-O digallate structure with a tetra- ortho -substituted diaryl ether bond, is described. The methodology involved an oxa-Michael addition/elimination reaction between a brominated ortho -quinone monoketal and a phenol with a hexahydroxydiphenoyl moiety in the presence of 18-crown-6 under dark conditions, followed by reductive aromatization. The existence of rotamers originating from the constructed ether moiety is discussed as well.