title: Modular Construction of Fluoroarenes from a New Difluorinated Building Block by Cross-Coupling/Electrocyclisation/Dehydrofluorination Reactions.
abstract: Palladium-catalysed coupling reactions based on a novel and easy-to-synthesise difluorinated organotrifluoroborate were used to assemble precursors to 6π-electrocyclisations of three different types. Electrocyclisations took place at temperatures between 90 and 240 °C, depending on the central component of the π-system; nonaromatic trienes were most reactive, but even systems that required the temporary dearomatisation of two arenyl subunits underwent electrocyclisation, albeit at elevated temperatures. Photochemical conditions were effective for these more demanding reactions. The package of methods delivered a structurally diverse set of fluorinated arenes, spanning a 20 kcal mol(-1) range of reactivity, by a flexible route.
authors.affiliation: WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK. jonathan.percy@strath.ac.uk.
authors.forename: Jonathan M
authors.initials: JM
authors.lastname: Percy
authors.affiliation: WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors.forename: Helena
authors.initials: H
authors.lastname: Emerson
authors.affiliation: WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors.forename: James W B
authors.initials: JW
authors.lastname: Fyfe
authors.affiliation: WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors.forename: Alan R
authors.initials: AR
authors.lastname: Kennedy
authors.affiliation: WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors.forename: Sergej
authors.initials: S
authors.lastname: Maciuk
authors.affiliation: WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors.forename: David
authors.initials: D
authors.lastname: Orr
authors.affiliation: WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors.forename: Lucie
authors.initials: L
authors.lastname: Rathouská
authors.affiliation: Allergic Inflammation DPU, GlaxoSmithKline Medicines Research Centre, Gunnels Wood Road, Stevenage, SG1 2NY, UK.
authors.forename: Joanna M
authors.initials: JM
authors.lastname: Redmond
authors.affiliation: WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors.forename: Peter G
authors.initials: PG
authors.lastname: Wilson
keywords: cross-coupling; density functional calculations; electrocyclic reactions; fluorine; palladium