Abstract
A stereoselective synthesis of the protected skipped all-syn pentaol 18 based on our γ-butyrolactone → 1,3-diol degradation is described. Lactone 7, readily accessible from L-glutamic acid, and the dibromoisobutene equivalent 6 were elaborated in three steps into bislactone 10 having four stereogenic centers. Oxidative degradation of both lactone moieties via a double Criegee rearrangement of a bis(peroxosulfonate) gave the diastereomerically pure tetraol 11. Ozonolytic cleavage of its C=C bond followed by chelation-controlled reduction with Zn(BH4)2 led to the fifth hydroxy group with ds ≥ 10:1.

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