Electrophilic C₁₂ building blocks for alkaloids: Formal total synthesis of (±)-maritidine

Silyl-protected benzyl alcohol derivatives and the salt 1 are used to form ortho-substituted C-12 electrophilic organoiron building blocks which are converted into a spirocyclic cyclohexenone to complete a formal total synthesis of (+/-)-maritidine (5). The choice of TBDPS protection was shown to be better than TIPS and compatible with ipso nucleophile addition to form a quaternary center. The reaction sequence is the first example of a successful application in the synthesis of an arylcyclohexadienyliron complex with an ortho-carbon substituent in the position required for Amaryllidaceae alkaloids of this type.