Abstract
AbstractQuinones 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.
Highlights
Hydrogen-bonding interactions have a substantial effect on the energetics of organic reactions by offering stabilizing interactions to transition structures and reactive intermediates.1 This stabilizing effect plays an important role in electron transfer chemistry, in which Hbonding—and, at the extreme, protonation—can substantially alter the thermodynamics and kinetics of this reaction.2 Hydrogen-bond-donor-coupled electron transfer is a process analogous to proton-coupled electron transfer (PCET), in which H-bonding interactions—in contrast to full proton transfer—are responsible for this modulation of the thermodynamics and kinetics
We present a brief description of PCET and its effect on electron transfer to quinones in biological systems
An overview of the literature precedent regarding the intermediacy of H
Summary
2a.5.3 Mechanistic analysis of HBD-coupled electron transfer using neutral ureas. 2a.5.5 Mechanistic analysis of HBD-coupled electron transfer using dicationic bis-amidinium salts. 2a.5.3 Mechanistic analysis of HBD-coupled electron transfer using neutral ureas. 2a.5.5 Mechanistic analysis of HBD-coupled electron transfer using dicationic bis-amidinium salts. 2a.5.9 Mechanistic analysis of HBD-coupled electron transfer using 55 formamidinium salts vi
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