Electrochemical pathway for intermolecular cross coupling

    ion

    At the end of 2018 Vapourtec launched the Ion electrochemical reactor. We’ve since had the exciting opportunity to explore the potential offered by electrochemical reactions in flow by collaborating with the following leading research groups:

         Wirth Group at Cardiff University, UK

    •       Polyzos Group at University of Melbourne, AUS

    •       New Path Molecular Research Ltd., Cambridge, UK

    New application note using the Ion Electrochemical reactor

    We now present a new application note prepared from work undertaken by New Path Molecular Research Ltd.  This research project uses the Vapourtec Ion electrochemical reactor for the reductive cross-electrophile coupling of organic halides, constructing a Csp2-Csp3 bond. After optimization of this key reaction, the desired product was afforded in a yield of 81%.

    In 2017, Pfizer revealed a reductive cross coupling reaction to construct Csp2-Csp3 bonds from organic halides in a batch electrochemical system (Perkins, Pedro, & Hansen, 2017). An electrochemical protocol was used to reduce a nickel catalyst (NiII to Ni0 or NiIII to NiII according to literature).  In the application note presented by Vapourtec this same reaction is optimised under continuous flow conditions using the Vapourtec Ion electrochemical reactor.

     

    Other published work using the Ion Electrochemical Reactor

    Previously published work using the Ion electrochemical reactor;

    Efficient Flow Electrochemical Alkoxylation of Pyrrolidine-1-carbaldehyde

    Nasser Amriaa, Ryan A. Skiltonb, Duncan Guthrieb, Thomas Wirth*a

    a School of Chemistry, Cardiff University, Park Place, Cardiff, CF10 3AT, UK

    b Vapourtec Ltd., 21 Park Farm Business Centre, Bury St Edmunds, IP28 6TS, UK

    In this paper, the methoxylation of pyrrolidine-1-carbaldehyde was reported using different alcohols. By adjusting the reaction conditions (electrode material, flow, current and solvent), 95% of starting material was oxydised to 2-methoxypyrrolidine-1-carbaldehyde with 2% dimethoxylated by-product. It was also found, that the alcohol chain length had a critical impact on the yield of the reaction; as the chain length increases, the methoxylation yield diminishes.

     

    Flow Electrochemical Cyclizations via Amidyl Radicals: Easy Access to Cyclic Ureas

    Nisar Ahmedaa,b*, Aggeliki Vgenopoulouaa

    a School of Chemistry, Cardiff University, Park Place, Cardiff, CF10 3AT, UK

    b School of Chemistry, University of Bristol, Bristol, BS8 1TS, UK

    This paper reports the electrosynthesis of cyclic ureas in high yields (89-95%) using the Ion Electrochemical reactor. In combination with the use of TEMPO, Wirth’s group functionalised double bonds of N-allylic ureas in continuous flow. The proposed mechanism suggests that, under electric current, a radical is formed at the amido nitrogen of the allylic urea, starting an intramolecular cyclation. The cyclic radical is then quenched with TEMPO, giving the final cyclic urea.

     

    Continuous Flow Electrochemical Generator of Hypervalent Iodine Reagents: Synthetic Applications

    Mohamed Elsherbiniaa, Bethan Winterson, Haifa Alharbi, Ana A. Folgueiras-Amador, Célina Génot and Thomas Wirth*a

    a School of Chemistry, Cardiff University, Park Place, Cardiff, CF10 3AT, UK

    Hypervalent iodine reagents are an environmentally friendly alternative to oxidant reagents containing heavy metals. The traditional route to synthesise hypervalent iodine reagents requires the use (in excess) of peroxides, Selectrfluor® or Oxone®. This paper presents an electrochemical alternative to generate hypervalent iodine compounds without hazardous chemical oxidants. The anodic oxidation of iodoarenes in flow reliably generated hypervalent iodine reagents.

     

     

    To read more about this application note click here

    To read more about the Ion electrochemical reactor click here

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