title: Stereocontrolled synthesis of 1,5-stereogenic centers through three-carbon homologation of boronic esters.
abstract: Allylic pinacol boronic esters are stable toward 1,3-borotropic rearrangement. We developed a Pd(II)-mediated isomerization process that gives di- or trisubstituted allylic boronic esters with high E selectivity. The combination of this method with lithiation-borylation enables the synthesis of carbon chains that bear 1,5-stereogenic centers. The utility of this method has been demonstrated in a formal synthesis of (+)-jasplakinolide.
authors.affiliation: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS (UK).
authors.forename: Phillip J
authors.initials: PJ
authors.lastname: Unsworth
authors.forename: Daniele
authors.initials: D
authors.lastname: Leonori
authors.forename: Varinder K
authors.initials: VK
authors.lastname: Aggarwal
mesh_terms: D001897:Boronic Acids / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D001897:Boronic Acids; D004952:Esters
keywords: 1,5-stereocenters; allylic boronic esters; asymmetric synthesis; lithiation-borylation; palladium