S. Ito*, W. Wang, K. Nozaki*
Polym. J. 2015, 47, 474–480. DOI: 10.1038/pj.2015.27
Abstract: As chain-growth polymerization generally forms aliphatic main chains containing units such as alkylene and alkenylene, the method has rarely been applied to the construction of arylene units. Thus, the formation/introduction of arylene groups via chain-growth polymerization remains a challenging subject in polymer chemistry. In this study, we report a formal aryne/ethylene copolymerization using [2.2.1]oxabicyclic alkenes as aryne equivalents. A palladium-catalyzed copolymerization of [2.2.1]oxabicyclic alkenes with ethylene followed by acid-promoted dehydration produced novel aryne/ethylene copolymers. The use of a bulky phosphine–sulfonate ligand was essential to obtain the desired copolymers with high molecular weight.