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Part I: New reactions of alpha-oxygenated hydroperoxides. Part II: Design, synthesis, and applications of a new class of twin-chain amphiphiles

Thomas J Fisher, University of Nebraska - Lincoln


Organic peroxides are a versatile functionality capable of a multitude of important synthetic transformations. Looking to expand their reactivity, we have identified and developed several new reactions of alpha-oxygenated hydroperoxides. These include a hypochlorite-mediated dehydration to give carboxylic esters, the mechanism of which likely proceeds through a novel heterolytic fragmentation of a chloroperoxide, and a one-pot ozonolysis/reduction/reductive amination protocol for the conversion of alkenes to amines. In the course of the latter, we have identified sodium triacetoxyborohydride as the first hydride reductant that is capable of selectively reducing a hydroperoxide in the presence of an aldehyde. Amphiphilic organic compounds play a vital role in myriad applications. One such application is in the fabrication of electrochemical gold-thiolate biosensors. Typically, self-assembled monolayers (SAMs) formed from single-chain amphiphiles are used for metal surface passivation and bioprobe immobilization in biosensor applications. However, SAMs made up of single-chain amphiphiles can form poorly ordered, unstable monolayers which leads to degraded sensor performance. We have developed a new class of twin-chain amphiphiles for biosensor applications which have fully functionalized termini as well as a nearly consistent cross-section down the length of the amphiphile. The new molecules provide an avenue to better performing, more stable, and reusable biosensors. As part of the synthesis of these amphiphiles, a new method for the synthesis of unsymmetrical tetraalkynylarenes was developed based upon consecutive, regioselective dual Sonogashira cross-couplings of a novel synthetic platform. We also describe mechanistic insights into cross-coupling reactions between silyl ketene acetals and aryl 1,2-ditriflates as part of our installation of bis ortho acetate synthons.

Subject Area

Organic chemistry

Recommended Citation

Fisher, Thomas J, "Part I: New reactions of alpha-oxygenated hydroperoxides. Part II: Design, synthesis, and applications of a new class of twin-chain amphiphiles" (2012). ETD collection for University of Nebraska - Lincoln. AAI3546598.