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Resonance promoted ring-opening metathesis polymerization of twisted amides

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Abstract

The living ring-opening metathesis polymerization (ROMP) of an unsaturated twisted amide using the third-generation Grubbs initiator is described. Unlike prior examples of ROMP monomers that rely on angular or steric strain for propagation, this system is driven by resonance destabilization of the amide that arises from geometric constraints of the bicyclic framework. Upon ring-opening, the amide can rotate and rehybridize to give a stabilized and planar conjugated system that promotes living propagation. The absence of other strain elements in the twisted amide is supported by the inability of a carbon analogue of the monomer to polymerize and computational studies that find resonance destabilization accounts for 11.3 kcal mol−1 of the overall 12.0 kcal mol−1 ring strain. The twisted amide polymerization is capable of preparing high molecular weight polymers rapidly at room temperature, and post-polymerization modification combined with 2D NMR spectroscopy confirms a regioirregular polymer microstructure.

Graphical abstract: Resonance promoted ring-opening metathesis polymerization of twisted amides

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Publication details

The article was received on 20 Jul 2019, accepted on 30 Aug 2019 and first published on 30 Aug 2019


Article type: Edge Article
DOI: 10.1039/C9SC03602D
Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY license
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    Resonance promoted ring-opening metathesis polymerization of twisted amides

    M. Xu, K. K. Bullard, A. M. Nicely and W. R. Gutekunst, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C9SC03602D

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