title: Highly functionalized tertiary-carbinols and carbinamines from the asymmetric γ-alkoxyallylboration of ketones and ketimines with the borabicyclodecanes.
abstract: The first asymmetric γ-alkoxyallylboration of representative ketones provides β-alkoxy tert-homoallylic alcohols 10 whose diastereoselectivities range from 99% syn (acetophenone) to 99% anti (pinacolone) both with high ee (>95%). This distribution is attributable to the c/t isomerization of the BBD reagents and the greater reactivity of 7 vs 1 and of aromatic vs alkyl ketones. A ketone-based direct synthesis of a fostriecin intermediate and the tert-amine 26 are reported, each with high selectivities.
authors.affiliation: Department of Chemistry, University of Puerto Rico , Rio Piedras, Puerto Rico 00931-3346, United States.
authors.forename: Lorell
authors.initials: L
authors.lastname: Muñoz-Hernández
authors.forename: Luis A
authors.initials: LA
authors.lastname: Seda
authors.forename: Bo
authors.initials: B
authors.lastname: Wang
authors.forename: John A
authors.initials: JA
authors.lastname: Soderquist
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D000588:Amines / Q000737:chemistry*; D001880:Boranes / Q000737:chemistry*; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D002384:Catalysis; D007097:Imines / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D011090:Polyenes / Q000138:chemical synthesis / Q000737:chemistry; D011753:Pyrones / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D000588:Amines; D001880:Boranes; D019086:Bridged Bicyclo Compounds, Heterocyclic; D007097:Imines; D007659:Ketones; D009570:Nitriles; D011090:Polyenes; D011753:Pyrones; C542835:ketimine; C040313:fostriecin