Citation
Walton, David Paul (2019) General Strategies for Visible-Light Decaging Based on Quinone Photochemistry. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/0793-KJ34. https://resolver.caltech.edu/CaltechTHESIS:02012019-134839099
Abstract
The design, synthesis, and photochemistry of several quinone based photoremovable protecting groups is reported. A visible light (400-600 nm) intramolecular photoreduction of 1,4-benzoquinones and 1,4-naphthoquinones mediated by amine and sulfide substituents was employed to launch a fast thermal lactonization step. Both the trimethyl lock and o-coumarinic acid lactonizations were incorporated into these designs. Quantum yields in air equilibrated solvents are moderate (Φ = 0.01-0.10), and chemical yields are generally quantitative. Detailed mechanistic studies reveal a mechanism distinct from typical n,π* quinone photochemistry. Biological applications and longer wavelength derivatives were further explored.
| Item Type: | Thesis (Dissertation (Ph.D.)) | |||||||||
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| Subject Keywords: | Photochemistry, organic chemistry, quinones, photocages, photoremovable protecting groups | |||||||||
| Degree Grantor: | California Institute of Technology | |||||||||
| Division: | Chemistry and Chemical Engineering | |||||||||
| Major Option: | Chemistry | |||||||||
| Thesis Availability: | Public (worldwide access) | |||||||||
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| Defense Date: | 30 January 2019 | |||||||||
| Non-Caltech Author Email: | dpw117 (AT) gmail.com | |||||||||
| Record Number: | CaltechTHESIS:02012019-134839099 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechTHESIS:02012019-134839099 | |||||||||
| DOI: | 10.7907/0793-KJ34 | |||||||||
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| Default Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 11382 | |||||||||
| Collection: | CaltechTHESIS | |||||||||
| Deposited By: | David Walton | |||||||||
| Deposited On: | 04 Feb 2019 22:33 | |||||||||
| Last Modified: | 04 Oct 2019 00:24 |
Thesis Files
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PDF (Thesis in PDF Form)
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