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Activation of Electron‐Deficient Quinones through Hydrogen‐Bond‐Donor‐Coupled Electron Transfer
Author(s) -
Turek Amanda K.,
Hardee David J.,
Ullman Andrew M.,
Nocera Daniel G.,
Jacobsen Eric N.
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201508060
Subject(s) - electron transfer , oxidizing agent , chemistry , photochemistry , hydrogen bond , electron transport chain , quinone , molecule , stereochemistry , organic chemistry , biochemistry
Quinones are important organic oxidants in a variety of synthetic and biological contexts, and they are susceptible to activation towards electron transfer through hydrogen bonding. Whereas this effect of hydrogen bond donors (HBDs) has been observed for Lewis basic, weakly oxidizing quinones, comparable activation is not readily achieved when more reactive and synthetically useful electron‐deficient quinones are used. We have successfully employed HBD‐coupled electron transfer as a strategy to activate electron‐deficient quinones. A systematic investigation of HBDs has led to the discovery that certain dicationic HBDs have an exceptionally large effect on the rate and thermodynamics of electron transfer. We further demonstrate that these HBDs can be used as catalysts in a quinone‐mediated model synthetic transformation.