Publications by authors named "David Kesselring"

Oxidation reactions are powerful tools for synthesis because they allow for the functionalization of molecules. Here, we present a general method for conducting these reactions on a microelectrode array in a site-selective fashion. The reactions are run as a competition between generation of a chemical oxidant at the electrodes in the array and reduction of the oxidant by a "confining agent" in the solution above the array.

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Conditions for a site-selective ceric ammonium nitrate oxidation have been developed. The reactions proceed nicely on both 1K- and 12K-microelectrode arrays. The procedure for developing the reactions was very simple and demonstrated that the same reagents used for a solution-phase reaction can be used for a related site-selective reaction on a microelectrode array.

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Article Synopsis
  • A new method has been created for selectively generating reactive N-acyliminium ion intermediates using a microelectrode array.
  • This method involves using an electroauxiliary to create a specific methoxylated amino acid before generating acid electrochemically, which helps in forming the N-acyliminium ion.
  • Key factors include the stability of the N-alpha-methoxyalkyl amide under basic conditions and the ability to conduct selective reactions on the microelectrode array using the electrogenerated acid.
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A series of silyl-substituted amino acids have been synthesized, inserted into peptides, and then employed as precursors for oxidatively generating reactive N-acyliminium ions. Both electrochemical and chemical oxidation procedures have been employed. N-Acyliminium ion generation in a solid-phase substrate as well as application to a small library of functionalized dipeptides has been demonstrated.

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