| dc.identifier.uri | http://hdl.handle.net/11401/77820 | |
| dc.description.sponsorship | This work is sponsored by the Stony Brook University Graduate School in compliance with the requirements for completion of degree. | en_US |
| dc.format | Monograph | |
| dc.format.medium | Electronic Resource | en_US |
| dc.language.iso | en_US | |
| dc.publisher | The Graduate School, Stony Brook University: Stony Brook, NY. | |
| dc.type | Dissertation | |
| dcterms.abstract | The Passerini three-component reaction is an isocyanide-based multicomponent reaction through which an aldehyde, a carboxylic acid, and an isocyanide form an α-acyloxycarboxamide motif. The Passerini reaction proceeds in one-pot, under mild reaction conditions, and is well suited for combinatorial chemistry and library design. The Passerini three-component reaction has been gaining recent interest in the field of polymer chemistry as a strategy to obtain higher structural complexity and functional diversity, which is desirable for the synthesis of advanced materials. Recognizing the potential of the Passerini three-component reaction, we are interested in the possibility of extending the scope of the reaction towards higher molecular weight and sterically bulky systems such as dendrimer synthesis. We are interested in exploring the combination of the convergent synthetic method and the Passerini three-component reaction in the synthesis of dendrimers. The convergent synthesis is an iterative process that begins at the periphery of the molecule and extends towards a focal point. The periphery groups are coupled to a branched monomer to form a wedge-shaped dendritic fragment, also known as a dendron. The final step of the convergent synthesis involves the coupling of dendrons to a core molecule. We envision that the Passerini reaction could be applied in the final step, in the coupling of three dendron components to form an α-acyloxycarboxamide scaffold as the core of the dendrimer. We have demonstrated the application of the Passerini three-component reaction in the convergent synthesis of dendrimers in a proof-of-concept experiment. In designing the experiments we anticipate that we will need dendrons that can tolerate a variety of conditions for functionalization at the apex. The Passerini components are derived from poly(alkyl ether) dendrons that have chemically robust alkyl ether linkages. We have demonstrated the synthesis of a second-generation surface-block dendrimer via the Passerini three-component reaction. Combining the convergent approach with the Passerini three-component reaction creates an opportunity for extending the current strategy towards dendrons of other branched repeat units and towards the synthesis of higher generation dendrimers. We are interested in pushing the limits of the convergent synthesis of dendrimers via the Passerini reaction and attain higher generation dendrimers through this approach. We anticipate that steric hindrance would be a factor in the synthesis of higher generation dendrimers. Separating the bulk of the branched repeat units from the apex branch point of the dendron with short linker groups may alleviate steric effects at the apex of the dendron. Through this process, we identified a substituent effect from the linker group that accelerates the convergent synthesis of dendrimers via the Passerini reaction. We were able to synthesize up to three-generations of dendrimers. The enhanced reactivity of an ether-substituted aldehyde component in the Passerini reaction provides a design principle for the convergent synthesis of higher generation dendrimers via the Passerini reaction. | |
| dcterms.available | 2017-09-26T16:56:26Z | |
| dcterms.contributor | Grubbs, Robert | en_US |
| dcterms.contributor | Rudick, Jonathan G | en_US |
| dcterms.contributor | Gang, Oleg | en_US |
| dcterms.contributor | Balija, Amy. | en_US |
| dcterms.creator | Jee, Jo-Ann | |
| dcterms.dateAccepted | 2017-09-26T16:56:26Z | |
| dcterms.dateSubmitted | 2017-09-26T16:56:26Z | |
| dcterms.description | Department of Chemistry. | en_US |
| dcterms.extent | 92 pg. | en_US |
| dcterms.format | Monograph | |
| dcterms.format | Application/PDF | en_US |
| dcterms.identifier | http://hdl.handle.net/11401/77820 | |
| dcterms.identifier | Jee_grad.sunysb_0771E_12402.pdf | en_US |
| dcterms.issued | 2015-05-01 | |
| dcterms.language | en_US | |
| dcterms.provenance | Submitted by Jason Torre (fjason.torre@stonybrook.edu) on 2017-09-26T16:56:26Z
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| dcterms.provenance | Made available in DSpace on 2017-09-26T16:56:26Z (GMT). No. of bitstreams: 1
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Previous issue date: 2015-05-01 | en |
| dcterms.publisher | The Graduate School, Stony Brook University: Stony Brook, NY. | |
| dcterms.subject | Chemistry | |
| dcterms.title | Convergent Synthesis of Dendrimers via the Passerini Three-Component Reaction | |
| dcterms.type | Dissertation | |
