Highly enantioselective oxidations of ketene dithioacetals leading to trans bis-sulfoxides

Ketene dithioacetals undergo a Sharpless-type asymmetric oxidation using (+)-DET, Ti((OPr)-Pr-i)(4), and cumene hydroperoxide to give the trans bis-sulfoxides 4a-f with essentially complete control of enantioselectivity and diastereoselectivity. The high enantioselectivity is a consequence of carrying out two asymmetric processes on the same substrate. However, this should lead to the formation of a small amount of the meso isomer but none was isolated. From monitoring the enantioselectivity of the monoxide over time, it was concluded that small amounts of the meso isomer must be formed. The inability to isolate this compound could be because it acted as a ligand on titanium and remained tightly bound even upon workup.