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General Strategies for Visible-Light Decaging Based on Quinone Photochemistry


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.


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.))
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)
Research Advisor(s):
  • Dougherty, Dennis A.
Thesis Committee:
  • Stoltz, Brian M. (chair)
  • Reisman, Sarah E.
  • Grubbs, Robert H.
  • Dougherty, Dennis A.
Defense Date:30 January 2019
Non-Caltech Author Email:dpw117 (AT)
Record Number:CaltechTHESIS:02012019-134839099
Persistent URL:
Related URLs:
URLURL TypeDescription from Ch 3.​Adapted from Ch 2.
Walton, David Paul0000-0002-9557-6461
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11382
Deposited By: David Walton
Deposited On:04 Feb 2019 22:33
Last Modified:04 Oct 2019 00:24

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