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Nonracemic allylic boronates through enantiotopic-group-selective cross-coupling of geminal bis(boronates) and vinyl
Bowman Potter1, Adam A Szymaniak, Emma K Edelstein
1Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
Abstract:
Under the influence of a chiral palladium catalyst, 1,1-bis(pinacolboronate) esters undergo asymmetric cross-coupling with bromoalkenes to generate nonracemic allyl boronates with high levels of enantioselectivity. The so-formed allyl boronates may be oxidized with hydrogen peroxide to provide secondary allylic alcohols or with nitrosobenzene to furnish nonracemic tertiary allylic alcohols. Mechanistic experiments suggest the operation of a pathway involving outer-sphere stereoinvertive transmetalation.
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