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

•Reaction conditions for Kumada style couplings were examined.•Slower addition of the organometallic gave more cross-coupled products.•Lower temperatures gave more homo-coupled product.

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.

Graphical abstractBy varying the temperature, and mode of addition of the organometallic reagent, it was possible to control the production of cross-coupled or homo-coupled products in a series of Palladium catalyzed reactions using fluorinated paracyclophanes.Figure optionsDownload full-size imageDownload as PowerPoint slide