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  4. Pd-Catalyzed Strain-Releasing Dyotropic Rearrangement: Ring-Expanding Amidofluorination of Methylenecyclobutanes
 
research article

Pd-Catalyzed Strain-Releasing Dyotropic Rearrangement: Ring-Expanding Amidofluorination of Methylenecyclobutanes

Yang, Baochao  
•
Yang, Guoqiang  
•
Wang, Qian
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2025
Journal of the American Chemical Society

Under the Pd(II)/Pd(IV) catalytic cycle, the cyclization of pent-4-en-1-amine derivatives typically yields either pyrrolidines or piperidines depending on the N-protecting group. We report herein an unprecedented Pd(II)-catalyzed oxidative domino process that converts readily accessible N-protected 2-(2-amidoethyl)-1-methylenecyclobutane derivatives to 1-fluoro-2-azabicyclo[3.2.1]octanes. This transformation constructs three chemical bonds under mild conditions [Pd(hfacac)2 (5.0 mol %), Selectfluor (2.0 equiv), MeCN, 60 °C, 10 min] through a domino sequence involving 5-exo-trig amidopalladation/Pd(II)-oxidation/chemoselective dyotropic rearrangement/C-F bond-forming reductive elimination. Notably, the cyclization mode remains independent of the N-protecting group under these conditions. Furthermore, diverse functional groups can be introduced at the bridgehead position of a bicyclic compound via an apparent anti-Bredt bridgehead iminium intermediate.

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Type
research article
DOI
10.1021/jacs.5c01108
Scopus ID

2-s2.0-85219218460

PubMed ID

40023786

Author(s)
Yang, Baochao  

École Polytechnique Fédérale de Lausanne

Yang, Guoqiang  

École Polytechnique Fédérale de Lausanne

Wang, Qian

École Polytechnique Fédérale de Lausanne

Zhu, Jieping  

École Polytechnique Fédérale de Lausanne

Date Issued

2025

Published in
Journal of the American Chemical Society
Volume

147

Issue

10

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LSPN  
FunderFunding(s)Grant NumberGrant URL

EPFL

Available on Infoscience
March 14, 2025
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/247813
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