Asymmetric polymerization using C1 resources

Abstract

ABSTRACT:Two examples of asymmetric alternating copolymerization, (1) the alternating copolymerization of ␣-olefins (monosubstituted ethenes) with carbon monoxide and (2) the alternating copolymerization of meso-epoxide with carbon dioxide, are described, and the meaning of chirality in polymer synthesis is emphasized.

Incorporation of ketone groups into poly(4‐hydroxystyrene)s main chain by radical copolymerization of 4‐(tert‐butoxy)styrene and 2,2‐diphenyl‐4‐methylene‐1,3‐dioxolane and their photoscission

“…These interesting points of polyketones have prompted the development of various synthetic approaches to them, which involves the transition metal‐catalyzed alternating copolymerization of carbon monoxide with α‐olefins such as ethylene, propylene, and styrene 11–15. Besides these simple olefinic compounds, various vinyl monomers having polar functionalities have become possible to be copolymerized with carbon monoxide due to the recent advances in catalysts 16–20.…”

Carbon Anionic Chiral Initiators for Asymmetric Anionic Polymerization of Achiral Isocyanates

“…The obtained poly(n-BI) showed positive or negative specific rotation with different solvent ( Table 1, Nos. 2,5,7,8). Although the absolute value of specific rotation of the polymers given in THF is much larger than that in toluene, whereas the polymers obtained in toluene have much larger molecular weight than that in THF.…”

“…[1][2][3] The optically active polymers investigated in the synthetic aspect are roughly classified into two types: one is the introduction of an asymmetric center of the monomer molecule into the polymer main chain and is one of the most employed methods, such as polymerization of optically active monomers represented by binaphthyl. 4,5 Other synthetic approaches for control of chirality of the repeating unit in the main chain, i.e., helix-senseselective type conformation of asymmetric polymerization of achiral monomers, [6][7][8] have been undertaken. Due to the limited and expensive source of the chiral monomer, the current research focuses on the latter.…”

Synthesis of a polyester macromonomer via the cobalt‐catalyzed alternating copolymerization of propylene oxide and carbon monoxide

“…In the course of our research on the metal‐catalyzed copolymerization of α‐olefins or epoxides with C1 materials such as CO and CO 2 ,9 we embarked on the alternating copolymerization of epoxide and carbon monoxide. The copolymerization was first reported by Furukawa et al in 1965 10.…”