Resonance promoted ring-opening metathesis polymerization of twisted amides.

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 st

SUBMITTER: Xu M 

PROVIDER: S-EPMC6993617 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature