The ACS Green Chemistry Institute Pharmaceutical Roundtable has identified a need for safer alternatives to the organic peracids and non-flammable chlorinated solvents which are routinely employed in oxidation processes. In our research collaboration we have employed electrochemistry, membrane emulsification and continuous processing in a combined approach to develop greener oxidation reactions for fine chemical and pharmaceutical synthesis. In 2016 we reported the development of a bench-top electrochemical flow reactor and its application in the generation of peroxodisulfate from non-hazardous ammonium sulfate. The on-site, on-demand nature of this technology negates the need for expensive transportation and storage of organic peracid or hydrogen peroxide solutions. We have recently extended this electrochemical methodology to allow the generation of the oxidant peroxomonosulfate through a residence time controlled reaction in continuous flow. The reactivity of electrochemically generated peroxosulfate solutions is highly dependent on the specific oxidant composition of the solution [S2O82-, SO52- and H2O2]. This composition is monitored by off-line redox colorimetry and in-line spectroscopy to ensure that the optimal oxidant is used for the targeted synthetic transformation. In this talk we will present recently developed applications of these sustainable reagents in important oxidation reactions such as the dihydroxylation of styrenes and alkyl alkenes, the Baeyer-Villiger oxidation of ketones into esters, and the transition metal catalyzed oxidation of alcohols.

On-demand electrochemical generation of oxidants and their applications in organic synthesis

254th National Meeting (2017)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.