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The precise control of monomer sequence and stereochemistry in copolymerization is of much interest and importance for the synthesis of functional polymers, but studies toward this goal have met with only limited success to date. We report herein the co‐syndiospecific alternating copolymerization of methoxyphenyl‐ and N , N ‐dimethylaminophenyl‐functionalized propylenes with styrene by half‐sandwich rare‐earth catalysts. This reaction efficiently afforded the corresponding functionalized propylene− alt −styrene copolymers with a perfect alternating sequence and excellent co‐syndiotacticity ( rrrr > 99%), thus constituting the first example of co‐stereospecific alternating copolymerization of polar and non‐polar olefins.

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