title: Palladium-catalyzed substitution and cross-coupling of benzylic fluorides.
abstract: Benzylic fluorides are suitable substrates for Pd(0)-catalyzed Tsuji-Trost substitution using carbon, nitrogen, oxygen, and sulfur nucleophiles and for cross-coupling with phenylboronic acid. For the bifunctional substrate 4-chlorobenzyl fluoride, fine-tuning of the reaction conditions allows for the regioselective displacement of either the chlorine or fluorine substituent. The leaving group ability of fluoride vs other groups displaced in substitution is CF(3)CO(2) ≈ p-NO(2)C(6)H(4)CO(2) ≈ OCO(2)CH(3) > F > CH(3)CO(2), a ranking similar to allylic fluorides under Pd catalysis.
authors.affiliation: University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA, UK.
authors.forename: George
authors.initials: G
authors.lastname: Blessley
authors.forename: Patrick
authors.initials: P
authors.lastname: Holden
authors.forename: Matthew
authors.initials: M
authors.lastname: Walker
authors.forename: John M
authors.initials: JM
authors.lastname: Brown
authors.forename: Véronique
authors.initials: V
authors.lastname: Gouverneur
mesh_terms: D001555:Benzene Derivatives / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D001555:Benzene Derivatives; D006845:Hydrocarbons, Fluorinated; D010165:Palladium