Cyclocopolymerization of α,ω-Dienes with Carbon Monoxide Catalyzed by (R,S)-BINAPHOS–Pd(II)

Abstract

Abstract Cyclocopolymerization of 1,4-pentadiene with carbon monoxide gave polyketone 3 in the presence of a Pd(II) catalyst bearing an unsymmetrical bidentate ligand, (R,S)-BINAPHOS {=(R)-2-(diphenylphosphino)-1,1′-binaphthalen-2′yl (S)-1,1′-binaphthalene-2,2′-diyl phsophite}. In the repeating unit of 3, exclusive formation of a cyclopentanone framework rather than cyclohexanone has been revealed by 13C NMR and IR spectroscopies. A single-unit analog 2 was prepared to identify the structure of 3. In the cyclopentanone unit of 3, the two substituents are cis and trans to each other in almost 1 : 1 ratio. The polymer 3 showed different behavior in thermal analysis from that of propene–CO alternating copolymer. 1,5-Hexadiene also afforded the corresponding cyclocopolymer 5. The molar optical rotation of polymer 3 was much lower than that of 5.