Copper(I)-Mediated 1,2-Metallate Rearrangements of 1-Metallated Glycals

Abstract

1,2-Metallate rearrangements involving reaction of 1-metallated glycals with organolithium reagents under copper(I) mediation give alkenylpolyol chains in 45-91% yield (19 examples). The reaction was applied to a formal synthesis of KRN7000 as well as a synthesis of a Δ^5,6-ceramide derivative.

1,2-metallate rearrangement - retro-[1,4]-Brook rearrangement - 1-metallated glycals - cuprates - organolithiums - KRN7000

References

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