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Published April 5, 2017 | Supplemental Material + Accepted Version
Journal Article Open

Mechanistic Studies of the Photoinduced Quinone Trimethyl Lock Decaging Process

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.

Additional Information

© 2017 American Chemical Society. Received: November 21, 2016; Published: February 15, 2017. This work was supported by the W. M. Keck Foundation. Additional support was provided by the Arnold and Mabel Beckman Foundation through the Caltech Beckman Institute Laser Resource Center. We thank Jay Winkler for technical assistance and helpful discussions, and Scott Virgil for assistance with studies of compound 1n.The authors declare no competing financial interest.

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Accepted Version - jacs_2E6b12007.pdf

Supplemental Material - ja6b12007_si_001.pdf

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August 19, 2023
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