title: Highly diastereo- and enantioselective allylboration of aldehydes using α-substituted allyl/crotyl pinacol boronic esters via in situ generated borinic esters.
abstract: Readily available, α-substituted allyl/crotyl pinacol boronic esters often give low E/Z selectivity (with Z favored) in reactions with aldehydes. We found that addition of nBuLi to the pinacol boronic ester followed by trapping of the alkoxide with TFAA leads to an intermediate allyl borinic ester which undergoes allylboration with very high E selectivity. The substrate scope includes primary to tertiary alkyl α-substituents, crotyl substrates, and the previously unreported β-methallyl pinacol boronic esters. The latter give very high Z selectivity under standard conditions which is completely reversed to high E selectivity under the new conditions. Monitoring the reaction by (11)B NMR confirmed that the reaction proceeds through a borinic ester intermediate.
authors.affiliation: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, United Kingdom.
authors.forename: Jack L-Y
authors.initials: JL
authors.lastname: Chen
authors.forename: Helen K
authors.initials: HK
authors.lastname: Scott
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: Hesse
authors.forename: Christine L
authors.initials: CL
authors.lastname: Willis
authors.forename: Varinder K
authors.initials: VK
authors.lastname: Aggarwal
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D001896:Boron Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D001897:Boronic Acids / Q000737:chemistry*; D004952:Esters / Q000737:chemistry*; D008968:Molecular Conformation; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D001896:Boron Compounds; D001897:Boronic Acids; D004952:Esters