Palladium/Benzoic Acid-Catalyzed Regio- and Stereoselective Polymerization of Internal Diynes and Diols through C(sp³)–H Activation

The C-H activation has been a hot research area in organic chemistry, and the most difficult one is the C(sp³)-H activation. Although the C-H activation has been introduced to the research of synthetic polymer chemistry, the polymerization developed based on C(sp³)-H activation is rarely reported, which will enrich the tools for the preparation of functional polymers. In this work, palladium/benzoic acid catalyzed polymerization of internal diynes and diols through C(sp³)-H activation was successfully established. Regio- and stereoregular functional poly(allylic ether)s with 100% <i>E</i>-isomers and high weight average molecular weights (<i>M</i>_w up to 33200) were prepared in excellent yield (98%). The reaction mechanism was unveiled with the assistance of density functional theory calculations. Furthermore, the thin films of polymers display high refractive indices and low optical dispersions. The polymer containing tetraphenylethene moiety displays the aggregation-enhanced emission feature and could be used to generate 2D fluorescent photopattern. Thus, this work not only establishes a powerful polymerization based on C(sp³)-H activation, but also furnishes functional polymers for diverse applications.