The role of geometry on regioselectivity and rate of fluorination of fluorene and diphenylmethane with Selectfluor™ F-TEDA-BF4

Abstract

Diphenylmethane and fluorene were used as target molecules in an investigation of the effect of the geometry of aromatic molecules on the regioselectivity and rate of fluorination with 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor™ F-TEDA-BF₄). In acetonitrile at 80 °C ring fluorination of diphenylmethane was accompanied by oxidation of the saturated carbon atom, while in trifluoroacetic acid only ring fluorination with an ortho–para regioselectivity of 1.8 ∶ 1 was observed. Fluorene was converted in acetonitrile as well as in trifluoroacetic acid into 2- and 4-fluoro substituted products in the relative ratio of 2 ∶ 1 and 1.2 ∶ 1, respectively. The reactions in acetonitrile obey a simple rate equation: v = d[F-TEDA]/dt = k₂ × [F-TEDA] × [Substrate] and the second order rate constants for the reactions in acetonitrile at 65 °C were determined; values of 0.6 × 10⁻⁴ M⁻¹ s⁻¹ for diphenylmethane and 35.5 × 10⁻⁴ M⁻¹ s⁻¹ for fluorene were obtained. The reaction rates for the various functionalisations of fluorene relative to those for diphenylmethane were found to be considerably influenced by the type of functionalisation. Relative rate factors (k_rel = k_2(fluorene)/k_{2(diphenylmethane)}) with values between 59 for fluorination and 712 for chlorination were determined, while the corresponding data for the biphenyl/diphenylmethane pair were only slightly dependent on the type of functionalisation. A reaction pathway involving electron transfer, thus forming cation radical intermediates, was proposed as the main process in the case of fluorination of fluorene with F-TEDA-BF₄.