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

Author(s) Choi, K.; Park, H.; Lee, C.
Journal J Am Chem Soc
Date Published 2018 Aug 09

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.

DOI 10.1021/jacs.8b05561
ISSN 1520-5126
Citation J Am Chem Soc. 2018.

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