The construction of mono- and bicyclic phosphate trimesters possessing divalent and multivalent activation and their subsequent use in the production of advanced polyol synthons is presented. The method highlights efforts to employ phosphate tethers as removable, functionally active tethers capable of multipositional activation and their subsequent role as leaving groups in selective cleavage reactions. The development of phosphate tethers represents an integrated platform for a new and versatile tether for natural product synthesis and sheds light on new approaches to the facile construction of small molecules.

Desymmetrization of a readily derived pseudo-C(2)-symmetric monocyclic phosphate via highly diastereoselective anti-S(N)2' allylic displacement reactions is reported. This method utilizes of a wide variety of zinc-derived organocuprates to afford E-1,2-syn-configured phosphate acid building blocks. Extension of this protocol to unsymmetric monocyclic phosphates exclusively yields 1,2-anti-configured products. Within this study, stereoelectronic factors, coupled with allylic strain, ultimately govern regio- and diastereoselective cuprate reactions, further substantiating the Corey mechanism for organocuprate additions into allylic esters. [reaction: see text]

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