Mechanistic Studies of the Photoinduced Quinone Trimethyl Lock Decaging Process.

Content Provider	Semantic Scholar
Author	Regan, Clinton Joseph Walton, David Paul Shafaat, Oliver S. Dougherty, Dennis A.
Copyright Year	2017
Abstract	Mechanistic studies of a general reaction that decages a wide range of substrates on exposure to visible light are described. The reaction involves a photochemically initiated reduction of a quinone mediated by an appended thioether. After reduction, a trimethyl lock system incorporated into the quinone leads to thermal decaging. The reaction could be viewed as an electron-transfer initiated reduction of the quinone or as a hydrogen abstraction-Norrish Type II-reaction. Product analysis, kinetic isotope effects, stereochemical labeling, radical clock, and transient absorption studies support the electron transfer mechanism. The differing reactivities of the singlet and triplet states are determined, and the ways in which this process deviates from typical quinone photochemistry are discussed. The mechanism suggests strategies for extending the reaction to longer wavelengths that would be of interest for applications in chemical biology and in a therapeutic setting.
Starting Page	4729
Ending Page	4736
Page Count	8
File Format	PDF HTM / HTML
Alternate Webpage(s)	http://authors.library.caltech.edu/74454/3/ja6b12007_si_001.pdf
PubMed reference number	28199106v1
Alternate Webpage(s)	https://doi.org/10.1021/jacs.6b12007
DOI	10.1021/jacs.6b12007
Journal	Journal of the American Chemical Society
Volume Number	139
Issue Number	13
Language	English
Access Restriction	Open
Subject Keyword	1,4-benzoquinone Isotopes Kinetics Light, Visible PQQ Cofactor Photochemistry Thioethers wavelength
Content Type	Text
Resource Type	Article