Electronic Activity Tuning of Acyclic Guanidines for Lactide Polymerization
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Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany
*E-mail: [email protected] (S.H.).
Abstract
Novel aromatic guanidine-based organocatalysts for the ring-opening of l-lactide were synthesized and applied in comprehensive polymerization experiments and kinetic studies. The introduction of electronically active substituents led to a significant change in activity by 2 orders of magnitude. The formed polylactide is featured with narrow polydispersity and high end-group fidelity, both characteristics that are typical for living polymerizations. Besides that, using linear free-energy relationships and DFT calculations revealed new insights into the polymerization mechanism. The formation of an adduct consisting of the catalyst and initiator/chain end turned out to be the rate-limiting step.
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(7)
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(49)
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(12)
, 1354-1358. https://doi.org/10.1016/j.tetlet.2016.02.050