Interplay of cascade oxidative cyclization and hydride shifts in the synthesis of the ABC spiroketal ring system of pectenotoxin-4.

Concepts: The formation of stereochemically defined bis-THF units through a double cyclization and a hydride-shift-initiated route to spiroketals is described (see scheme; Xc=chiral auxiliary). The resulting sequence has been used in a synthesis of the C1-16 fragment of the naturally occurring antitumor agent pectenotoxin-4.