Organic Chemistry

Alkyne Polymers from Stable Butatriene Homologues: Controlled Radical Polymerization of Vinylidenecyclopropanes

Authors

Abstract

Controlled polymerization of cumulenic monomers represents a promising yet underdeveloped strategy towards well-defined alkyne polymers. Here we report a stereoelectronic effect-inspired approach using simple vinylidenecyclopropanes (VDCPs) as butatriene homologues in controlled radical ring-opening polymerizations. While being thermally stable, VDCPs mimic butatrienes via conjugation of the cyclopropane ring. This leads to exclusive terminal-selective propagation that affords a highly structurally regular alkynebased backbone, featuring complete ring-opening and no backbiting regardless of polymerization conditions.

Content

Thumbnail image of VDCP-1117-chemrxiv.pdf

Supplementary material

Thumbnail image of SI-1116-r6.pdf
supporting information
Procedures, characterizations, GPC traces, NMR spectra, computation details.