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DOI: 10.1055/a-2558-0268
Synthesis of Bicyclic Piperidines Enabled by a Palladium(IV) Dyotropic Rearrangement
Pd-Catalyzed Strain-Releasing Dyotropic Rearrangement: Ring-Expanding Amidofluorination of Methylenecyclobutanes.
J. Am. Chem. Soc. 2025;
147: 8969-8977
DOI: 10.1021/jacs.5c01108

Significance
Zhu and co-workers report a strain-releasing rearrangement of methylenecyclobutanes under Pd(II)/Pd(IV) catalysis to generate 2-azabicyclo[3.2.1]octanes. This motif is present in many alkaloid natural products. This work expands on the application of Pd(IV) dyotropic rearrangements within the context of domino chemistry.
Comment
Upon initial aminopalladation of the methylenecyclobutane, a neopentyl Pd(II) species is generated. In the absence of Selectfluor, the authors observed retro-carbopalladation and subsequent β-H elimination. This highlights the requirement for a rapid oxidation to Pd(IV) for this system to undergo dyotropic rearrangement.
Publication History
Article published online:
22 April 2025
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