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  4. Diverting the 5-exo-Trig Oxypalladation to Formally 6-endo-Trig Fluorocycloetherification Product through 1,2-O/Pd(IV) Dyotropic Rearrangement
 
research article

Diverting the 5-exo-Trig Oxypalladation to Formally 6-endo-Trig Fluorocycloetherification Product through 1,2-O/Pd(IV) Dyotropic Rearrangement

Gong, Jing  
•
Wang, Qian  
•
Zhu, Jieping  
2023
Journal of the American Chemical Society

Pd-catalyzed cyclizative functionalization of γ-hydroxyalkenes affords tetrahydrofuran derivatives via a key 5-exo-trig oxypalladation step. Herein, we report a palladium(II)-catalyzed, Selectfluor-mediated formal 6-endo-trig fluorocycloetherification of γ-hydroxyalkenes for the synthesis of functionalized tetrahydropyrans. Mechanistically, an σ-alkyl-Pd(II) intermediate resulting from the 5-exo-trig oxypalladation process is isolated and characterized by X-ray crystallographic analysis. Its oxidation with Selectfluor to Pd(IV) triggers the chemoselective 1,2-O/Pd(IV) dyotropic rearrangement affording, after C−F bond-forming reductive elimination, the tetrahydropyrans with concurrent generation of a tertiary carbon−fluorine bond. The occurrence of this 1,2- positional interchange is further evidenced by trapping the rearranged quaternary C(sp3)−Pd bond by an internal nucleophile that is materialized by the development of a Pd(II)-catalyzed oxidative bis-heterocyclization of alkenes.

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Type
research article
DOI
10.1021/jacs.3c06158
Author(s)
Gong, Jing  
Wang, Qian  
Zhu, Jieping  
Date Issued

2023

Published in
Journal of the American Chemical Society
Volume

145

Issue

29

Start page

15735

End page

15741

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LSPN  
Available on Infoscience
July 28, 2023
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/199391
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