Total Synthesis of (-)-Alloaristoteline, (-)-Serratoline, and (+)-Aristotelone

Article abstract of DOI:10.1021/jo00055a007

The Aristotelia alkaloids (-)-alloaristoteline (4), (-)-serratoline (12), and (+)-aristotelone (13) have been prepared as summarized in Scheme IV.Thus, via the method of Stevens, (1S)-(-)-β-pinene (9) and 3-indolylacetonitrile (10) were coupled by a Hg(NO3)2-mediated Ritter reaction followed by reduction of the resulting imine to give (+)-makomakine (11).An intramolecular Friedel-Crafts reaction delivered (+)-aristoteline (3), which was oxidized by reaction with oxygen and platinum.Reduction of the intermediate hydroperoxide delivered alkaloid 12.Base-catalyzed skeletal rearrangement of 12 provided alkaloid 13, which was reduced with LiAlH4 to obtain a mixture of secondary alcohols, 14a,b.Treatment of each of these alcohols with HCl in methanol afforded (-)-alloaristoteline (4).