Palladium catalyzed cross- and homo-coupling reactions of 4-Halo-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophanes with various organometallic reagents

An investigation of palladium catalyzed Kumada type reactions between various Grignard reagents and mono-substituted octafluoroparacyclophane derivatives revealed that by varying the reaction temperature, and mode of addition of the Grignard reagent, it was possible to influence whether the major product was the cross-coupled, or the homo-coupled (reductive dimer) paracyclophane product. This provides an improved methodology to prepare aryl substituted paracyclophanes, and additionally an alternative route to the unusual and rare di-cyclophane skeleton. Analogous reactions with alkyl lithium reagents were also explored, resulting in the generation of some previously unreported octafluoroparacyclophane products.