p-Bromoaryl- and ω-bromoalkyl-VA-PNBs: suitable starting materials for the functionalization of vinylic addition polynorbornenes via palladium-catalyzed cross-coupling reactionsElectronic supplementary information (ESI) available: Additional tables with experimental data, and IR and solution or solid state NMR spectra of the polymers. See DOI: 10.1039/c6ra23123c

• Main Authors: Martínez-Arranz, Sheila, Sánchez-Pérez, Eduardo, Molina de la Torre, Jesús A, Pérez-Ortega, Ignacio, Albéniz, Ana C
• Format: Article
• Language: English
• ISSN: 2046-2069
• DOI: 10.1039/c6ra23123c

New vinylic addition polynorbornenes (VA-PNBs) with a variable amount of pendant 4-bromoaryl groups have been synthesized by homo- and copolymerization with norbornene of 2-(4-bromophenyl)-5-norbornene catalyzed by [Ni(C 6 F 5 ) 2 (SbPh 3 ) 2 ]. These polymers can be transformed by Pd-catalyzed cross coupling reactions into VA-PNBs with pendant diaryl (Suzuki), alkenyl and ketoalkyl (Stille) and amino (Buchwald-Hartwig) groups. Although the cross-coupling reactions of alkylhalides are more difficult, (ω-bromobutyl)-VA-PNBs can also be functionalized by a Suzuki reaction with arylboronic acids. This results open up new ways of post-polymerization functionalization of VA-PNBs, quite attractive for their robust, thermally stable and transparent skeleton. New routes to functionalize the robust VA-polynorbornene skeleton by Pd-catalyzed cross-coupling reactions use p -bromoaryl- and ω-bromoalkyl-VA-PNBs as versatile starting materials.