title: Direct Access to β-Fluorinated Aldehydes by Nitrite-Modified Wacker Oxidation.
abstract: An aldehyde-selective Wacker-type oxidation of allylic fluorides proceeds with a nitrite catalyst. The method represents a direct route to prepare β-fluorinated aldehydes. Allylic fluorides bearing a variety of functional groups are transformed in high yield and very high regioselectivity. Additionally, the unpurified aldehyde products serve as versatile intermediates, thus enabling access to a diverse array of fluorinated building blocks. Preliminary mechanistic investigations suggest that inductive effects have a strong influence on the rate and regioselectivity of the oxidation.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA.
authors.forename: Crystal K
authors.initials: CK
authors.lastname: Chu
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA.
authors.forename: Daniel T
authors.initials: DT
authors.lastname: Ziegler
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA.
authors.forename: Brian
authors.initials: B
authors.lastname: Carr
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA.
authors.forename: Zachary K
authors.initials: ZK
authors.lastname: Wickens
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA. rhg@caltech.edu.
authors.forename: Robert H
authors.initials: RH
authors.lastname: Grubbs
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D054879:Halogenation; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009573:Nitrites / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D006845:Hydrocarbons, Fluorinated; D009573:Nitrites
keywords: aldehydes; fluorine; oxidation; palladium; regioselectivity