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Synfacts 2025; 21(05): 473
DOI: 10.1055/a-2558-0268
Metals in Synthesis

Synthesis of Bicyclic Piperidines Enabled by a Palladium(IV) Dyotropic Rearrangement

Contributor(s):
Mark Lautens 
,
Colton E. Johnson
Yang B, Yang Q, Wang Q, Zhu J *. Ecole Polytechnique Fédérale de Lausanne, Switzerland
Pd-Catalyzed Strain-Releasing Dyotropic Rearrangement: Ring-Expanding Amidofluorination of Methylenecyclobutanes.

J. Am. Chem. Soc. 2025;
147: 8969-8977
DOI: 10.1021/jacs.5c01108
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Keywords

palladium catalysis - dyotropic rearrangement - N-heterocycles - palladium(IV)

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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