Studies towards the synthesis of functionalized aryl fluorides : transition metal catalyzed cross-coupling and fluorination of organoboron reagents

• Main Author: Sun, Duo
• Language: English
• Published: University of British Columbia 2013
• Online Access: http://hdl.handle.net/2429/43839

This thesis covers several synthetic approaches to the generation of highly functionalized aryl fluorides. PtCl₂(SMe₂)₂ and PtCl₂(DMSO)₂ have been applied to catalytic methylation of polyfluoroaryl imines as user-friendly precatalysts. These complexes have demonstrated high selectivity for ortho C-F activation and subsequent functionalization, exhibiting high functional group tolerance while proving more thermal, moisture and air stable than our original catalyst, [PtMe₂(SMe₂)]₂. Nickel-catalyzed Suzuki-Miyaura and Negishi cross-coupling reactions allow rapid functionalized of C-F bonds; we have been able to obtain a variety of highly functionalized aryl-, heteroaryl-, and alkyl-substituted aryl fluoride molecules under mild reaction conditions. Furthermore, we have described a novel fluorination procedure that employs organoboron reagents and electrophilic fluorine sources. This method is rapid, high yielding and can be carried out without inert atmosphere protection and dry solvents.