Divergence between Organometallic and Single-Electron-Transfer Mechanisms in Copper(II)-Mediated Aerobic C–H Oxidation

2013 ◽  
Vol 135 (26) ◽  
pp. 9797-9804 ◽  
Author(s):  
Alison M. Suess ◽  
Mehmed Z. Ertem ◽  
Christopher J. Cramer ◽  
Shannon S. Stahl
Keyword(s):  
Electron Transfer ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Transfer Mechanisms

scholarly journals Radical Biocatalysis: Using Non-Natural Single Electron Transfer Mechanisms to Access New Enzymatic Functions

Synlett ◽  
2019 ◽  
Vol 31 (03) ◽  
pp. 248-254 ◽  
Author(s):  
Todd K. Hyster
Keyword(s):  
Electron Transfer ◽  
Active Sites ◽  
Hydrogen Atom Transfer ◽  
Single Electron ◽  
Great Promise ◽  
Single Electron Transfer ◽  
Radical Intermediates ◽  
Redox Activation ◽  
Transfer Mechanisms ◽  
Ground State Electron

Exploiting non-natural reaction mechanisms within native enzymes is an emerging strategy for expanding the synthetic capabilities of biocatalysts. When coupled with modern protein engineering techniques, this approach holds great promise for biocatalysis to address long-standing selectivity and reactivity challenges in chemical synthesis. Controlling the stereochemical outcome of reactions involving radical intermediates, for instance, could benefit from biocatalytic solutions because these reactions are often difficult to control by using existing small molecule catalysts. General strategies for catalyzing non-natural radical reactions within enzyme active sites are, however, undeveloped. In this account, we highlight three distinct strategies developed in our group that exploit non-natural single electron transfer mechanisms to unveil previously unknown radical biocatalytic functions. These strategies allow common oxidoreductases to be used to address the enduring synthetic challenge of asymmetric hydrogen atom transfer.1 Introduction2 Photoinduced Electron Transfer from NADPH3 Ground State Electron Transfer from Flavin Hydroquinone4 Enzymatic Redox Activation in NADPH-Dependent Oxidoreductases5 Conclusion

Reversal of Polarity by Catalytic SET Oxidation: Synthesis of Azabicyclo[m.n.o]alkanes via Chemoselective Reduction of Amidines

2021 ◽  
Author(s):  
Sundarababu Baskaran ◽  
Kirana D V ◽  
Kanak Kanti Das
Keyword(s):  
Electron Transfer ◽  
Stereoselective Synthesis ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Catalytic Method ◽  
One Pot ◽  
Oxidative System ◽  
Oxidation Synthesis

A one-pot catalytic method has been developed for the stereoselective synthesis of cyclopropane-fused cyclic amidines using CuBr2/K2S2O8 as an efficient single electron transfer (SET) oxidative system. The generality of this...

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