Experimental and Theoretical Studies on Iron-Promoted Oxidative Annulation of Arylglyoxal with Alkyne: Unusual Addition and Migration on the Aryl Ring

Chen Hsun Hung, Parthasarathy Gandeepan, Lin Chieh Cheng, Liang Yu Chen, Mu Jeng Cheng, Chien Hong Cheng

Research output: Contribution to journalArticlepeer-review

14 Citations (Scopus)

Abstract

An Fe(III)-promoted oxidative annulation reaction was developed for the synthesis of 1,2-naphthoquinones. A variety of substituted arylglyoxals and internal alkynes undergo the transformation in the presence of FeCl3 at room temperature to afford the 1,2-naphthoquinone products in good yields in a short reaction time. Interestingly, the products show unusual pseudomigration of the substituent on the arene ring of arylglyoxals. A possible mechanism involving Fe(III)-promoted formation of a vinyl cation from arylglyoxal and alkyne, electrophilic addition of the vinyl cation to the ipso carbon of the aryl group to give a spiral intermediate, and then migration of the keto carbon to the ortho carbon was proposed as key steps and verified using quantum mechanics.

Original languageEnglish
Pages (from-to)17015-17021
Number of pages7
JournalJournal of the American Chemical Society
Volume139
Issue number47
DOIs
Publication statusPublished - 2017 Nov 29

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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