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  • Review Article
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Asymmetric reactions involving aryne intermediates

Nature Reviews Chemistry volume 7, pages 496–510 (2023)Cite this article

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Abstract

Although arynes are usually considered fleeting intermediates, they are highly valuable synthons because they enable the introduction of aromatic rings and the simultaneous formation of new bonds at two sites. Although catalytic reactions using transition metals are excellent method for constructing complex polycyclic aromatic molecules in a single step, the use of asymmetric catalysis for the capture of arynes remains a crucial goal for the progress of aryne chemistry. Catalytic asymmetric reactions of arenes are challenging, requiring sufficient interactions between the neutral and highly reactive short-lived aryne intermediates in a stereo-controlled fashion. In addition, spontaneous decomposition, as well as side reactions, has hindered their development and, until recently, highly enantioselective reactions using arynes had remained elusive. This Review highlights asymmetric reactions using arynes, featuring diastereoselective, enantioselective and catalytic enantioselective reactions.

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Fig. 1: General strategies for stereoselective reactions involving aryne intermediates.
Fig. 2: Diastereoselective intermolecular or intramolecular cycloaddition reactions of arynes and arynophiles.
Fig. 3: Tandem cycloaddition reactions.
Fig. 4: Intramolecular cycloadditions with concomitant formation of a single carbon–carbon bond.
Fig. 5: Arene ene reaction with concomitant formation of a single carbon–carbon bond.
Fig. 6: α-Arylations by chiral nucleophiles.
Fig. 7: Diastereoselective and enantioselective synthesis of axially chiral biaryls.
Fig. 8: Catalytic enantioselective synthesis of helicene and α-arylation of ketone.

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Acknowledgements

The author gratefully acknowledges a Grant-in-Aid for Scientific Research (B) (22H02081), a Grant-in-Aid for Challenging Exploratory Research (22K19035) and a Toshiaki Ogasawara Memorial Foundation.

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  1. Department of Chemistry, Graduate School of Science, Osaka Metropolitan University, Sakai, Osaka, Japan

    Ken Kamikawa

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Kamikawa, K. Asymmetric reactions involving aryne intermediates. Nat Rev Chem 7, 496–510 (2023). https://doi.org/10.1038/s41570-023-00485-y

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