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Toward Perfect Regiocontrol for β-Selective Cyclopolymerization Using a Ru-Based Olefin Metathesis Catalyst

Jung, Kijung and Kim, Kunsoon and Sung, Jong-Chan and Ahmed, Tonia S. and Hong, Soon Hyeok and Grubbs, Robert H. and Choi, Tae-Lim (2018) Toward Perfect Regiocontrol for β-Selective Cyclopolymerization Using a Ru-Based Olefin Metathesis Catalyst. Macromolecules, 51 (12). pp. 4564-4571. ISSN 0024-9297. https://resolver.caltech.edu/CaltechAUTHORS:20180608-101413686

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Abstract

Ru-based metathesis catalysts employed in cyclopolymerization (CP) of 1,6-heptadiyne derivatives have promoted regioselective α-addition to alkynes, forming various conjugated polyenes containing exclusively five-membered repeat units. Recently, we discovered that a new chelated Ru catalyst could promote regioselective β-addition to produce analogous polyenes containing six-membered rings with moderate to good β-selectivity. Since then, we have focused our research on pursuing more active and β-selective regiocontrol to produce conjugated polymers with excellent β-selectivity, with a much broader range of monomers. Herein, we demonstrate highly β-selective CP by combining a new dithiolate-chelated Ru-based catalyst with weakly coordinating pyridine additives, which significantly enhance the conversion and β-selectivity. An in-depth mechanistic investigation by ^1H NMR revealed a prominent role for the additives, which improve the stability of the propagating carbene.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/acs.macromol.8b00969DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/acs.macromol.8b00969PublisherSupporting Information
ORCID:
AuthorORCID
Hong, Soon Hyeok0000-0003-0605-9735
Grubbs, Robert H.0000-0002-0057-7817
Choi, Tae-Lim0000-0001-9521-6450
Additional Information:© 2018 American Chemical Society. Received: May 6, 2018; Revised: May 28, 2018; Published: June 7, 2018. The financial support from Creative Research Initiative Program and the Nano-Material Technology Development Program through NRF is acknowledged. K.K. is supported by NRF-Global Ph.D. Fellowship program (Grant NRF-2015H1A2A1033766). We thank NCIRF and NICEM at SNU for supporting ^(13)C NMR experiments and LINC at Sogang University for supporting HR-MS experiments. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
National Research Foundation of KoreaNRF-2015H1A2A1033766
Issue or Number:12
Record Number:CaltechAUTHORS:20180608-101413686
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180608-101413686
Official Citation:Toward Perfect Regiocontrol for β-Selective Cyclopolymerization Using a Ru-Based Olefin Metathesis Catalyst. Kijung Jung, Kunsoon Kim, Jong-Chan Sung, Tonia S. Ahmed, Soon Hyeok Hong, Robert H. Grubbs, and Tae-Lim Choi. Macromolecules 2018 51 (12), 4564-4571. DOI: 10.1021/acs.macromol.8b00969
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86914
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:08 Jun 2018 18:37
Last Modified:03 Oct 2019 19:49

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