title: Catalytic enantioselective addition of organoboron reagents to fluoroketones controlled by electrostatic interactions.
abstract: Organofluorine compounds are central to modern chemistry, and broadly applicable transformations that generate them efficiently and enantioselectively are in much demand. Here we introduce efficient catalytic methods for the addition of allyl and allenyl organoboron reagents to fluorine-substituted ketones. These reactions are facilitated by readily and inexpensively available catalysts and deliver versatile and otherwise difficult-to-access tertiary homoallylic alcohols in up to 98% yield and >99:1 enantiomeric ratio. Utility is highlighted by a concise enantioselective approach to the synthesis of the antiparasitic drug fluralaner (Bravecto, presently sold as the racemate). Different forms of ammonium-organofluorine interactions play a key role in the control of enantioselectivity. The greater understanding of various non-bonding interactions afforded by these studies should facilitate the future development of transformations that involve fluoroorganic entities.
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: KyungA
authors.initials: K
authors.lastname: Lee
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: Daniel L
authors.initials: DL
authors.lastname: Silverio
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Torker
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: Daniel W
authors.initials: DW
authors.lastname: Robbins
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: Fredrik
authors.initials: F
authors.lastname: Haeffner
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: Farid W
authors.initials: FW
authors.lastname: van der Mei
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: Amir H
authors.initials: AH
authors.lastname: Hoveyda
mesh_terms: D000438:Alcohols; D000475:Alkenes / Q000737:chemistry; D001895:Boron / Q000737:chemistry* / Q000378:metabolism; D002384:Catalysis; D005461:Fluorine / Q000737:chemistry*; D007202:Indicators and Reagents; D007659:Ketones / Q000737:chemistry* / Q000378:metabolism; D009930:Organic Chemicals / Q000737:chemistry; D055672:Static Electricity; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D000475:Alkenes; D007202:Indicators and Reagents; D007659:Ketones; D009930:Organic Chemicals; D005461:Fluorine; D001895:Boron