Synthetic and Biosynthetic Studies on FR900482 and Mitomycin C: An Efficient and Stereoselective Hydroxymethylation of an Advanced Benzazocane Intermediate

We report a simple, efficient, and stereoselective Mukaiyama aldol approach to install the key hydroxymethyl moiety into the benzazocane
framework of FR900482. Synthetic investigations revealed that the reaction is highly dependent upon the electronics of the aromatic ring. This
approach enabled the economical introduction of a [13C] label to study the biosynthesis of these structurally and biogenetically related natural
products. Epimerization of the initially formed β-hydroxy ketone may enable access to mitomycin C or FR900482 biosynthetic congeners.