March 4, 2011

Anodic Coupling Reactions: Exploring the Generality of Curtin−Hammett Controlled Reactions

Alison Redden and Kevin D. Moeller

Org. Lett., 2011, 13 (7), 1678–1681

Intramolecular anodic olefin coupling reactions can be compatible with the presence of dithioketal protecting groups even though the dithioketal oxidizes at a lower potential than either of the groups participating in the cyclization. In such cases, product formation is controlled by the Curtin−Hammett Principle. In this study, the generality of such reactions is examined along with the use of alternative reaction conditions to suppress unwanted side reactions.


September 13, 2010

Intramolecular Anodic Olefin Coupling Reactions: Use of the Reaction Rate to Control Substrate/Product Selectivity

Hai-Chao Xu and Kevin D. Moeller

Angew. Chem. Int. Ed. 2010, 49, 8004–8007

Look out—it’s a trap! The anodic coupling of olefins with amine trapping groups to form proline and pipecolic acid derivatives with a quaternary α carbon atom (see scheme) was successful despite the significantly lower oxidation potential of the product relative to that of either functional group in the substrate: owing to the very fast cyclization, the oxidation potential of the substrate is lower than that of the product.


May 12, 2010

Anodic Coupling Reactions and the Synthesis of C-Glycosides

Guoxi Xu and Kevin D. Moeller

Org. Lett. 2010, 12(11), 2590-2593

A convenient, two-step procedure has been developed for converting sugar derivatives into C-glycosides containing a masked aldehyde functional group. The chemistry takes advantage of an anodic coupling reaction between an electron-rich olefin and an alcohol. The sequence works for the formation of both furanose and pyranose derivatives if less polarized vinyl sulfide derived radical cation intermediates are used. With more polarized enol ether derived radical cations, the cyclizations work best for the formation of furanose derivatives where the rate of five-membered ring formation precludes elimination reactions triggered by the radical cation.