Computational Study on the Synergic Effect of Brønsted Acid and Hydrogen-Bonding Catalysis for the Dearomatization Reaction of Phenols with Diazo Functionality

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  • Yanagawa Mai
    Graduate School of Pharmaceutical Sciences, Chiba University
  • Kobayashi Mayu
    Graduate School of Pharmaceutical Sciences, Chiba University
  • Ikeda Mitsuru
    Graduate School of Pharmaceutical Sciences, Chiba University
  • Harada Shingo
    Graduate School of Pharmaceutical Sciences, Chiba University
  • Nemoto Tetsuhiro
    Graduate School of Pharmaceutical Sciences, Chiba University Molecular Chirality Research Center, Chiba University

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<p>Catalytic dearomative transformations of phenol variants via an ipso-Friedel-Crafts reaction could provide a straightforward method for the rapid assembly of functionalized spiromolecules as versatile synthetic scaffolds. We previously reported a dearomative spirocyclization reaction by merging Brønsted acid and hydrogen-bonding catalysis. However, it was unclear how the reaction proceeded and how the synergic effect was triggered. Described herein are the computational studies used to elucidate the reaction mechanism. Such calculations indicated that the applied catalysts, maleic acid and Schreiner’s thiourea, work cooperatively. The synergic effect enabled the chemoselectivity to interconvert between phenol dearomatization and O–H insertion, which is a major side reaction. This investigation also revealed that not only does the Schreiner’s thiourea catalyst serve as a hydrogen bonding donor, but the sulfur atom in thiourea possesses a general base function. The dual functional support of the thiourea along with maleic acid would thus realize the chemoselective prioritization of dearomatization over the O–H insertion reaction under mild conditions.</p>

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