N‐Heterocyclic Carbene‐Catalyzed Umpolung of Alkynyl 1,2‐Diketones

Authors:

Abstract
The umpolung of alkynyl 1,2‐diketones via N‐heterocyclic carbene (NHC) catalysis was achieved for the first time, allowing the rapid access to a large variety of synthetically and pharmaceutically important α‐pyrones under very mild conditions. A completely new NHC‐catalyzed umpolung pattern involving an O‐acylated allenolate as the key intermediate was proposed. Moreover, an unprecedented reaction pathway, featured by a series of group migrations and new bond formation, was postulated to demonstrate the formation of the products. magnified image
Funding Information
  • Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000)
  • NSFC (21402199 and 21502192)
  • Chinese Recruitment Program of Global Experts

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