Haobing Wang, Yanan Zhao, M. Nishiura
Jul 25, 2019
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0
Influential Citations
34
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Journal
Journal of the American Chemical Society
Abstract
The precise control of regio- and stereochemistry in the cyclopolymerization of heteroatom-functionalized α,ω-dienes is of much interest and importance, but has remained a challenge to date. We report herein the regio-, diastereoselective and stere-oregular cyclopolymerization of ether- and thioether-functionalized 1,6-heptadienes by a half-sandwich scandium catalyst. The polymerization of 4-benzyloxy-1,6-heptadiene selectively afforded the corresponding benzyloxy-functionalized cyclic polymer composed of 1,2,4-cis-substituted-ethylenecyclopentane (ECP) microstructures in a isospecific fashion (95% mmm). In contrast, the polymerization of 4-phenylthio-1,6-heptadiene exclusively yielded 1,2-trans-1,4-cis-ECP units with high isotacticity (95% rrr). The DFT calculations revealed that an interaction between the scandium atom in the catalyst and the heteroatom in a diene monomer played an important role in controlling the regio- and stereochemistry of the diene cyclopolymerization. The copolymerization of functionalized 1,6-heptadienes with ethylene has also been achieved in a controlled fashion.