1,2-Rearrangement from o-Quinols to Multisubstituted Catechols via Retro Diels-Alder Reaction of o-Quinol Dimers

Riichi Hashimoto, Kengo Hanaya, Takeshi Sugai, Shuhei Higashibayashi

Research output: Contribution to journalArticlepeer-review

Abstract

The 1,2-rearrangement of o-quinols has been a long-standing unsolved problem since 1958. Although the rearrangement is expected to be useful for syntheses of catechol derivatives, it is hampered by many competing reactions and has not been developed as a useful methodology. Here, we succeeded in settling this problem by a first systematic thorough investigation, establishing the 1,2-rearrangement as a cascade reaction with a retro Diels-Alder reaction from o-quinol dimers. This is a useful strategy for syntheses of substituted catechols used as synthetic building blocks for bioactive compounds and material molecules. o-Quinol dimers were synthesized by improved oxidative hydroxylation of substituted phenols followed by spontaneous Diels-Alder reaction. The dimers then underwent the retro Diels-Alder reaction to regenerate the o-quinols followed by 1,2-rearrangement under neutral heating conditions at an appropriate temperature depending on the migratory substituent, furnishing substituted catechols in good yields. The competing reactions such as an elimination of a substituent or α-ketol rearrangement were minimized by controlling the reaction temperature.

Original languageEnglish
Pages (from-to)663-672
Number of pages10
JournalBulletin of the Chemical Society of Japan
Volume95
Issue number4
DOIs
Publication statusPublished - 2022

Keywords

  • 1,2-Rearrangement
  • o-Quinol
  • Substituted catechols

ASJC Scopus subject areas

  • Chemistry(all)

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