A Cation-Dependent Dual Activation Motif for Anionic Ring-Opening Polymerization of Cyclic Esters

A new organocatalyst for the ring-opening polymerization of lactones has been identified. Under the tested conditions, the anions of 2,2′-bisindole promote fast, living polymerizations (as short as 10 ms) which are selective for chain elongation over transesterification (Đ ≤ 1.1). While structurally...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2022-05, Vol.144 (19), p.8439-8443
Main Authors: Jadrich, Caleb N., Pane, Vince E., Lin, Binhong, Jones, Gavin O., Hedrick, James L., Park, Nathaniel H., Waymouth, Robert M.
Format: Article
Language:English
Subjects:
Anions
Cations
Esters
Lactones
Polymerization
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Summary:A new organocatalyst for the ring-opening polymerization of lactones has been identified. Under the tested conditions, the anions of 2,2′-bisindole promote fast, living polymerizations (as short as 10 ms) which are selective for chain elongation over transesterification (Đ ≤ 1.1). While structurally related to (thio)­urea anion catalysts, anions of 2,2′-bisindole activate the monomer via the counterion rather than through hydrogen bonding. This new activation motif enables modulation of the polymerization rate by 2 orders of magnitude by changing the counterion.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.2c01436