All Publications

  • Aqueous Amine-Tolerant [2+2] Photocycloadditions of Unactivated Olefins. Journal of the American Chemical Society Mansson, C. M., Burns, N. Z. 2022

    Abstract

    The Kochi-Salomon reaction is the only photochemical [2+2] cycloaddition capable of combining two electronically unactivated olefins into a cyclobutane. Yet, the reaction has remained largely unexplored and suffers many drawbacks, most notably an intolerance to Lewis/Bronsted basic amines and amides. Since these groups are ubiquitous in biologically active pharmaceuticals, an amine-tolerant Kochi-Salomon reaction would greatly facilitate rapid exploration of novel drug scaffolds. Herein, we disclose a transformation that is run in water with the most widely available Cu(II) salts and mineral acids. Furthermore, we apply this methodology to synthesize a variety of amine-containing cyclobutanes, including known and novel pharmacological analogues.

    View details for DOI 10.1021/jacs.2c08778

    View details for PubMedID 36269089

  • Mechanochemical synthesis of an elusive fluorinated polyacetylene. Nature chemistry Boswell, B. R., Mansson, C. M., Cox, J. M., Jin, Z., Romaniuk, J. A., Lindquist, K. P., Cegelski, L., Xia, Y., Lopez, S. A., Burns, N. Z. 2020

    Abstract

    Polymer mechanochemistry has traditionally been employed to study the effects of mechanical force on chemical bonds within a polymer backbone or to generate force-responsive materials. It is under-exploited for the scalable synthesis of wholly new materials by chemically transforming the polymers, especially products inaccessible by other means. Here we utilize polymer mechanochemistry to synthesize a fluorinated polyacetylene, a long-sought-after air-stable polyacetylene that has eluded synthesis by conventional means. We construct the monomer in four chemical steps on gram scale, which involves a rapid incorporation of fluorine atoms in an exotic photochemical cascade whose mechanism and exquisite stereoselectivity were informed by computation. After polymerization, force activation by ultrasonication produces a gold-coloured, semiconducting fluoropolymer. This work demonstrates that polymer mechanochemistry is a valuable synthetic tool for accessing materials on a preparative scale.

    View details for DOI 10.1038/s41557-020-00608-8

    View details for PubMedID 33349696