title: Rapid access to β-trifluoromethyl-substituted ketones: harnessing inductive effects in Wacker-type oxidations of internal alkenes.
abstract: We present a practical trifluoromethyl-directed Wacker-type oxidation of internal alkenes that enables rapid access to β-trifluoromethyl-substituted ketones. Allylic trifluoromethyl-substituted alkenes bearing a wide range of functional groups can be oxidized in high yield and regioselectivity. The distance dependence of the regioselectivity was established by systematic variation of the number of methylene units between the double bond and the trifluoromethyl group. The regioselectivity enforced by traditional directing groups could even be reversed by introduction of a competing trifluoromethyl group. Besides being a new powerful synthetic method to prepare fluorinated molecules, this work directly probes the role of inductive effects on nucleopalladation events.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 (USA).
authors.forename: Michael M
authors.initials: MM
authors.lastname: Lerch
authors.forename: Bill
authors.initials: B
authors.lastname: Morandi
authors.forename: Zachary K
authors.initials: ZK
authors.lastname: Wickens
authors.forename: Robert H
authors.initials: RH
authors.lastname: Grubbs
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D016227:Benzoquinones / Q000737:chemistry; D002384:Catalysis; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D016227:Benzoquinones; D006845:Hydrocarbons, Fluorinated; D007659:Ketones; C004532:quinone; D010165:Palladium
keywords: alkenes; ketones; palladium; regioselectivity; trifluoromethyl group