Formylphenoxy group

The first total synthesis of the 14-membered para ansa cyclopeptide alkaloid (-)-nummularine F was accomplished in the laboratory of M.M. Joullie. The A/3 nitrogen atom was introduced by using the Henry reaction between the 4-formylphenoxy group and the anion of nitromethane, followed by reduction of the nitro group to the corresponding amine. The epimeric benzyl alcohols did not pose a problem since they were dehydrated at the end of the synthetic sequence to give the C1-C2 double bond. 

Perfluorinated BSubPc bearing axial m-formylphenoxy group 196 [99] was used for preparation conjugates with fullerene (Scheme 51) as tunable molecular scaffolds for intramolecular electron and energy transfer processes [110]. The azome-thine ylide formed by treatment of the formyl derivative 196 with A -methylglycine gives the conjugate with fullerene 197 (44 %) in a dipolar 1,3-cycloaddition (Prato reaction). 

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