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ON-SURFACE CYCLOAROMATIZATION

3 + 3 makes the ring

Nature Synthesis volume 1, pages 260–261 (2022)Cite this article

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Ring-forming reactions are at the heart of organic synthesis. Now, phenylene rings are synthesized from two isopropyl moieties on a gold surface. Resolving the intermediates of this (3+3) cycloaromatization reaction with atomic force microscopy offers mechanistic insight into the dimerization process.

Now, writing in Nature Synthesis, Kinikar et al. introduce a method to build a phenylene ring on a gold surface by forming two carbon–carbon bonds between two isopropyl moieties of the precursor molecules2. This dimerization process involves a (3+3) cycloaromatization reaction. While previous cycloaromatization reactions require the use of unsaturated functional groups, such as alkenes or alkynes, this ring-forming reaction fuses carbon fragments that are initially sp3-hybridized. Some (3+3) cycloaddition reactions for obtaining heterocycles are known3; however, this isopropyl dimerization is unprecedented, not only in the field of on-surface synthesis, but in synthetic chemistry more generally.

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Fig. 1: Selected synthetic methods for obtaining a six-membered ring.

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Author notes

  1. Twitter: @depena33; @Leo_Gross_IBM

Authors and Affiliations

  1. Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, Santiago de Compostela, Spain

    Diego Peña

  2. IBM Research – Zurich, Rüschlikon, Switzerland

    Leo Gross

Authors
  1. Diego Peña
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  2. Leo Gross
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Correspondence to Diego Peña or Leo Gross.

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Peña, D., Gross, L. 3 + 3 makes the ring. Nat. Synth 1, 260–261 (2022). https://doi.org/10.1038/s44160-022-00041-4

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