Galloyl-derived orthoquinones as reactive partners in nucleophilic additions and Diels-Alder dimerizations: A novel route to the dehydrodigalloyl linker unit of agrimoniin-type ellagitannins

Orthochloranil-mediated oxidation of galloyl monoethers furnishes the derived orthoquinones in excellent yield. These reactive electrophiles participate in a variety of nucleophilic addition reactions with heteroatomic and carbanionic partners. In addition, Lewis acid-mediated dimerization of the orthoquinones provides an efficient route to dehydrodigalloyl-type diaryl ether units characteristic of several ellagitannin natural products. The implications for ellagitannin biosynthesis and gallotannin-protein covalent attachment are discussed.