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

• Published in: Journal of fluorine chemistry 2015-07, Vol.175, p.1-5
• Main Author: Roche, Alex J.
• Format: Article
• Language: English
• Subjects: Dicyclophane; Kumada reaction; Octafluoro[2.2]paracyclophane
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2015.02.016

By 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. •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.