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.


January 20, 2011

Site-Selectively Functionalizing Microelectrode Arrays: The Use of Cu(I)-Catalysts

Jennifer Bartels, Peng Lu, Karl Maurer, Amy V. Walker, and Kevin D. Moeller

Langmuir, 2011, 27 (17), pp 11199–11205

Site-selective Cu(I)-catalyzed reactions have been developed on microelectrode arrays. The reactions are confined to preselected electrodes on the arrays using oxygen as the confining agent. Conditions initially developed for the Cu(I)-catalyzed click reaction have proven general for the coupling of amine, alcohol, and sulfur nucleophiles to both vinyl and aryl iodides. Differences between reactions run on 1-K arrays and reactions run on 12-K arrays can be attributed to the 1-K array reactions being divided cell electrolyses and the 12-K array reactions being undivided cell electrolyses. Reactions on the 12-K arrays benefit from the use of a non-sugar-derived porous reaction layer for the attachment of substrates to the surface of the electrodes. The reactions are sensitive to the nature of the ligand used for the Cu catalyst.


January 20, 2011

Site-Selective, Cleavable Linkers: Quality Control and the Characterization of Small Molecules on Microelectrode Arrays

Bi, Bo; Huang, Richard Y.-C.; Maurer, Karl; Chen, Ceng; Moeller, Kevin D.

Journal of Organic Chemistry 2011, 76(21), 9053-9059

A “safety-catch” linker strategy has been used to release a portion of the products of a Diels-Alder reaction conducted on a microelectrode array for characterization of stereochem.  The attachment and cleavage of org. compds. from the surface of selected electrodes in the array can be accomplished by site-selective generation of base or acid at the electrode.  It was found that the surface of the array had a minor influence on the stereochem. of the Diels-Alder reaction, leading to slightly more of the exo-product relative to a similar soln.-phase reaction.