Electrochemistry Vs. Photochemistry: A Mechanistic Comparison of the Nucleophilic Trapping of Radical Cations from Electron-Rich Olefin

Thursday, 28 May 2015: 08:45
PDR 5 (Hilton Chicago)
M. D. Graaf and K. D. Moeller (Washington University in St. Louis)
The reactivity of electrochemically generated radical cations towards various nucleophiles have been investigated extensively.1 Complementary, the area of photoredox catalysis has made a significant contribution to the use of radical ions in organic synthesis.2 The use of these photoredox catalysts, in comparison with our electrochemical methods, has provided great insight into the behavior of radical cations. Although both of these methods efficiently produce radical cations, the mechanistic differences can have dramatic effects. As a result, the products obtained from identical substrates can vary immensely. Herein we report the mechanistic comparison of radical cations generated electrochemically and those generated photochemically.

1 a) Campbell, J. M.; Xu, H. C.; Moeller, K. D. JACS, 2012 , 134, 18338 b) Xu, H. C.; Campbell, J. M.; Moeller, K. D. JOC, 2014 , 79, 379
2 Schultz, D. M. and Yoon, T. P. Science, 2014 , 343, 985