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Synthesis of a Molecular Charm Bracelet via Click Cyclization and Olefin Metathesis Clipping

Clark, Paul G. and Guidry, Erin N. and Chan, Wing Yan and Steinmetz, Wayne E. and Grubbs, Robert H. (2010) Synthesis of a Molecular Charm Bracelet via Click Cyclization and Olefin Metathesis Clipping. Journal of the American Chemical Society, 132 (10). pp. 3405-3412. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20100408-145007341

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Abstract

We describe the synthesis of a polycatenated cyclic polymer, a structure that resembles a molecular charm bracelet. Ruthenium-catalyzed ring-opening metathesis polymerization of an aminocontaining cyclic olefin monomer in the presence of a chain transfer agent generated an α,ω-diazide functionalized polyamine. Cyclization of the resulting linear polyamine using pseudo-high-dilution coppercatalyzed click cyclization produced a cyclic polymer in 19% yield. The click reaction was then further employed to remove linear contaminants from the cyclic polymer using azide- and alkyne-functionalized scavenging resins, and the purified cyclic polymer product was characterized by gel permeation chromatography, ^1H NMR spectroscopy, and IR spectroscopy. Polymer hydrogenation and conversion to the corresponding polyammonium species enabled coordination and interlocking of diolefin polyether fragments around the cyclic polymer backbone using ruthenium-catalyzed ring-closing olefin metathesis to afford a molecular charm bracelet structure. This charm bracelet complex was characterized by ^1H NMR spectroscopy, and the catenated nature of the small rings was confirmed using two-dimensional diffusion-ordered NMR spectroscopy.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja9090337DOIArticle
http://pubs.acs.org/doi/full/10.1021/ja9090337?cookieSet=1PublisherArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2010 American Chemical Society. Published In Issue March 17, 2010. Article ASAP February 16, 2010. Received: October 22, 2009. We thank Professor Daniel J. O’Leary, Dr. David VanderVelde, Dr. Andrew J. Boydston, Dr. John. B. Matson, and Yan Xia for helpful discussions. The work was supported by the Office of Naval Research through its MURI program and the NSF (NSF CHE-0809418). W.Y.C. acknowledges the NSERC of Canada for a postdoctoral fellowship.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)UNSPECIFIED
NSFCHE-0809418
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
Issue or Number:10
Record Number:CaltechAUTHORS:20100408-145007341
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20100408-145007341
Official Citation:Synthesis of a Molecular Charm Bracelet via Click Cyclization and Olefin Metathesis Clipping Paul G. Clark, Erin N. Guidry, Wing Yan Chan, Wayne E. Steinmetz, Robert H. Grubbs Journal of the American Chemical Society 2010 132 (10), 3405-3412
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:17908
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:08 Apr 2010 22:39
Last Modified:03 Oct 2019 01:35

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