Syntheses of α,β-Epoxy Silyl Ketones

Article abstract of DOI:10.1002/hlca.19890720210

The synthesis of the α,β-epoxy-acylsilanes 1 and 2 starting from the allylic silyl alcohols (E)- and (Z)-3, respectively, by epoxidation with t-BuOOH/VO(acac)2 followed by oxidation with Collins reagent (CrO3/pyridine) in up to 70percent overall yields, is described.The acid-catalyzed rearrangement of the epoxy-silyl alcohols 4A+B and 5A+B led to the novel unstable diastereomeric α-silyl-β-hydroxy-aldehydes 9 and 10, respectively.The structure of 10 was established by X-ray crystal-structure analysis of the corresponding alcohol 11.