title: Nonracemic allylic boronates through enantiotopic-group-selective cross-coupling of geminal bis(boronates) and vinyl halides.
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.
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
authors.forename: Bowman
authors.initials: B
authors.lastname: Potter
authors.forename: Adam A
authors.initials: AA
authors.lastname: Szymaniak
authors.forename: Emma K
authors.initials: EK
authors.lastname: Edelstein
authors.forename: James P
authors.initials: JP
authors.lastname: Morken
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D001897:Boronic Acids / Q000737:chemistry*; D002384:Catalysis; D006219:Halogens / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D000475:Alkenes; D001897:Boronic Acids; D006219:Halogens; D010165:Palladium