Cyclopentanone ring expansion leading to functionalized delta-lactams: short synthesis of simple sedum alkaloids

Org Lett. 2007 Jul 5;9(14):2673-6. doi: 10.1021/ol070960r. Epub 2007 Jun 12.

Abstract

Monosubstituted epoxides react with (cyclopentenyloxy)trimethylsilane to afford, after subsequent oxidative fragmentation, a pair of diastereomeric 8-membered iodolactones. When these lactones are separately treated with sodium azide, followed by reduction over Lindlar's catalyst, lactone ring contraction yields 6-membered monosubstituted lactams. When (R)-1,2-epoxypentane is used in this 5 + 3 - 2 overall ring expansion sequence, one final step involving delta-lactam to piperidine reduction yields natural (-)-halosaline and (-)-epihalosaline in five steps and 12% and 23% overall yields, respectively.