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Synthesis of interlocked molecules by olefin metathesis

Citation

Clark, Paul Gregory (2011) Synthesis of interlocked molecules by olefin metathesis. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:07292010-112948436

Abstract

A large body of work in the Grubbs group has focused on the development of functional-group tolerant ruthenium alkylidene catalysts that perform a number of olefin metathesis reactions. These catalysts have seen application in a wide range of fields, including classic total synthesis as well as polymer and materials chemistry. One particular family of compounds, interlocked molecules, has benefitted greatly from these advances in catalyst stability and activity. This thesis describes several elusive and challenging interlocked architectures whose syntheses have been realized through the utilization of different types of ruthenium-catalyzed olefin metathesis reactions. Ring-closing olefin metathesis has enabled the synthesis of a [c2]daisy-chain dimer with the ammonium binding site near the cap of the dimer. A deprotonated DCD possessing such a structural attribute will more forcefully seek to restore coordinating interactions upon reprotonation, enhancing its utility as a synthetic molecular actuator. Dimer functionalization facilitated incorporation into linear polymers, with a 48% size increase of an unbound, extended analogue of the polymer demonstrating slippage of the dimer units. Ongoing work is directed at further materials studies, in particular, exploring the synthesis of macroscopic networks containing the DCD units and analyzing the correlation between molecular-scale extension-contraction manipulations and resulting macro-scale changes. A “clipping” approach to a polycatenated cyclic polymer, a structure that resembles a molecular “charm bracelet”, has been described. The use of ring-opening metathesis polymerization of a carbamate monomer in the presence of a chain transfer agent allowed for the synthesis of a linear polymer that was subsequently functionalized and cyclized to the corresponding cyclic analogue. This cyclic polymer was characterized through a variety of techniques, and subjected to further functionalization reactions, affording a cyclic polyammonium scaffold. Diolefin polyether fragments were coordinated and “clipped” around the ammonium sites within the polymer backbone using ring-closing olefin metathesis, giving the molecular “charm bracelet”. Confirmation of the interlocked nature of the product was achieved via 1H NMR spectroscopy and two-dimensional diffusion ordered NMR spectroscopy. A simple strategy for a one-pot, multi-component synthesis of polyrotaxanes using acyclic diene metathesis polymerization was developed. The polyrotaxanes were characterized by traditional 1H NMR spectroscopy as well as size exclusion chromatography, and the interlocked topology was confirmed using two-dimension diffusion-ordered NMR spectroscopy. The dynamic, self-correcting nature of the ADMET polymerization was also explored through the equilibration of a capped polyammonium polymer in the presence of dibenzo-24-crown-8 ether and olefin metathesis catalysts. The efficiency and ease with which these mechanically interlocked macromolecules can be assembled should facilitate rapid modulation to achieve versatile polyrotaxane architectures. Flexible, switchable [c2]daisy-chain dimers (DCDs) were synthesized, where the macromer ammonium binding site was adjacent to the crown-type recognition structure and separated from the cap by an alkyl chain. A DCD of this topology is expected to have an extended structure in the bound conformation (when the ammonium was coordinated to the crown). Several different macromer candidates were designed to allow access to DCDs with flexible alkyl chains between the ammonium binding site and the cap, and a number of synthetic routes were explored in an effort to access these challenging materials. While the first generation DCD structure proved to be unstable due to a labile ester linkage, work is continuing toward the development of several cap structures in an effort to replace the ester linkage with an ether linkage, which, in the second generation model systems, has proven much more stable to the acidic and basic conditions necessary to induce switching of the dimeric architecture. One of the efforts in our lab is directed at the synthesis of 18F-labeled nanoparticles to be used as tumor imaging agents in positron emission tomography. We have been working to optimize fluorine incorporation while minimizing NP crosslinking. Because of evidence of NP side-reactions with the potassium carbonate base, we have begun to use potassium benzoate solid-state beads. To analyze the fluorinated NPs, various sorbents were explored. It was found that silica sorbents rapidly reacted and bound to the NPs, while the NPs remained unreactive and mobile on alumina. Further analysis of the NPs has been accomplished using 2D-DOSY NMR spectroscopy. Future work with the NPs will involve a systematic evaluation of the role of water on the extent of fluorination, as well as functionalization of the NPs with Cy5.5 dye for use in studies on eyes to be done in collaboration with researchers at the Mayo Clinic.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Interlocked, Click, Polymer, Catenane, Rotaxane
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Grubbs, Robert H.
Thesis Committee:
  • Dervan, Peter B. (chair)
  • Tirrell, David A.
  • Heath, James R.
Defense Date:1 July 2010
Record Number:CaltechTHESIS:07292010-112948436
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:07292010-112948436
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:5981
Collection:CaltechTHESIS
Deposited By: Paul Clark
Deposited On:14 Sep 2010 21:18
Last Modified:26 Dec 2012 04:29

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