Total Synthesis of (−)-Dihydrosporothriolide Utilizing an Indium-Mediated Reformatsky–Claisen Rearrangement

The
asymmetric synthesis of (−)-dihydrosporothriolide (1), a biologically active bis-γ-butyrolactone, is described,
that proceeds through a d-proline-catalyzed asymmetric aminooxylation,
indium-mediated Reformatsky–Claisen rearrangement of an α,α-dibromoacetate
derivative, and diastereoselective dihydroxylation. The route requires
no protective group manipulation and allows the concise seven-step
synthesis of 1 from n-octanal.