General Strategies for Visible-Light Decaging Based on Quinone Photochemistry

Author: Walton, David Paul

Year: 2019

Degree: Dissertation (Ph.D.)

Advisor: Dougherty, Dennis A.

Committee Members: Stoltz, Brian M.; Reisman, Sarah E.; Grubbs, Robert H.; Dougherty, Dennis A.

Option: Chemistry

DOI: 10.7907/0793-KJ34

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.

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