Rhodium-Catalyzed Tandem Addition-Cyclization-Rearrangement of Alkynylhydrazones with Organoboronic Acids.

Transition metal-mediated catalysis routinely enables substrates of multiple π-systems to be efficiently coupled with various carbon nucleophiles along with simultaneous ring formation. This transformation, however, remains unexplored in connection with pericyclic processes. Reported here is a protocol for cycloalkene synthesis based on the merger of rhodium catalysis and a retro-ene reaction. The approach allows alkyne-tethered hydrazones and organoboronic acids to undergo a cascade of addition-cyclization-rearrangement reactions to provide cycloalkene products. The process is initiated by the rhodium-catalyzed addition-cyclization and completed with the allylic diazene rearrangement. The reaction can also be rendered asymmetric by using chiral diene ligands for the rhodium catalyst, whereby enantioselective addition to the C═N bond establishes the C-N stereocenter whose chirality is transferred to an allylic C-H center via suprafacial rearrangement.

• Publication year

  2018

• Venue

  Journal of the American Chemical Society

• Publication date

  2018-08-03

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1021/jacs.8b05561PMID 30075068
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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