Various α,β-unsaturated carbonyl compounds, such as acrylates and acrylamides, were quantitatively introduced to the terminal chain end of poly(phenylacetylene)s by C-C bond formation with terminal organorhodium(I) species formed in the living polymerization of phenylacetylenes with a rhodium-based multicomponent catalytic system that we have recently developed, when these carbonyl compounds were used as terminating reagents. This enables the facile and versatile synthesis of stereoregular telechelic poly(phenylacetylene)s with various functional groups at both the initial and terminal chain ends because the components of aryl boronic acid derivatives used as initiators in our multicomponent catalytic system are quantitatively introduced to the initiating end of the resulting polymer.
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