Copper-Mediated Oxidative Fluorination of Aryl Stannanes with Fluoride

Abstract

A regiospecific method for the oxidative fluorination of aryl stannanes using tetrabutylammonium triphenyldifluorosilicate (TBAT) and copper(II) triflate is described. This reaction is robust, uses readily available reagents, and proceeds via a stepwise protocol under mild conditions (60 °C, 3.2 h). Broad functional group tolerance, including arenes containing protic and nucleophilic groups, is demonstrated.

18F-Deoxyfluorination of Phenols via Ru π-Complexes

“…A variety of functional groups is tolerated, most importantly basic amines ( 7b , c , i , l ) which can present a major limitation to several available radiofluorination methods. 14 , 15 , 19 Protic functional groups ( 7e , j , n ) are unproblematic and phenolic hydroxyl groups can be selectively deoxyfluorinated in the presence of unprotected aliphatic alcohols without affecting carbinol stereochemistry ( 7h , l ). Additionally, several heterocyclic scaffolds, including pyrimidines ( 7m ), indoles ( 7o ), and quinolines ( 7k ) are good substrates for the reaction.…”

Copper-Mediated Radiofluorination of Arylstannanes with [18F]KF

“…However, to date, the major limitation in this field is that existing methods for the fluorination 16,17 and radiofluorination 18,19 of arylstannanes require electrophilic fluorine sources (e.g., F 2 , N -fluoropyridinium salts, N -fluorobenzenesulfonimide, Selectfluor) (Scheme 1a). 20 These reagents are much more expensive and less available than fluoride (particularly in the 18 F form). Furthermore, electrophilic radiofluorination methods result in products with dramatically lower specific activity (ratio of 18 F/ 19 F), which greatly reduces imaging sensitivity.…”

Chemie der Positronenemissionstomographie: Aktuelle Fortschritte bei 11C‐, 18F‐, 13N‐ und 15O‐Markierungsreaktionen

“…2016 berichteten Murphy et al. über die Kupfer‐vermittelte oxidative Fluorierung von Arylstannanen mit Fluorid unter Verwendung von TBAT und Kupfer(II)triflat . Im gleichen Jahr entwickelten Sanford, Scott et al.…”