Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 539-544 |
| Number of pages | 6 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 55 |
| Issue number | 2 |
| DOIs | |
| State | Published - Jan 11 2016 |
| Externally published | Yes |
Funding
This work was supported by the NIH (GM043214 to E.N.J.) and the DOE (DE-SC0009565 to D.G.N.), by an NSF predoctoral fellowship to A.K.T., and by an NIH post-doctoral fellowship to D.J.H. We thank Robert Knowles for many helpful discussions.
Keywords
- catalysis
- electron transfer
- hydrogen bonding
- oxidation
- quinones