Repository logo

Infoscience

  • English
  • French
Log In
Logo EPFL, École polytechnique fédérale de Lausanne

Infoscience

  • English
  • French
Log In
  1. Home
  2. Academic and Research Output
  3. Journal articles
  4. Apparent 6-endo-trig Carbofluorination of Alkenes Enabled by Palladium-Based Dyotropic Rearrangement
 
Loading...
Thumbnail Image
research article

Apparent 6-endo-trig Carbofluorination of Alkenes Enabled by Palladium-Based Dyotropic Rearrangement

Gong, Jing
•
Wang, Qian
•
Zhu, Jieping  
November 16, 2022
Angewandte Chemie International Edition

Alkene difunctionalization featuring an intramolecular carbometallation step has been developed into a powerful transformation in organic synthesis. The 5-exo-trig carbometallation is in general highly favored over the alternative 6-endo-trig cyclization. We report herein a formal 6-endo-trig carbofluorination protocol by combining the conventional 5-exo-trig carbopalladation with a chemoselective 1,2-aryl/Pd dyotropic rearrangement. Treatment of 2-(2-alkylallyloxy)phenyl boronic acid derivatives in the presence of a catalytic amount of Pd(dba)(2), 4,4 '-di-tert-butyl-2,2 '-bipyridine and Selectfluor affords chromanes with concurrent generation of a tertiary alkyl fluoride function. A sigma-alkyl-Pd-II species resulting from the 5-exo-trig carbopalladation process is isolated and characterized by X-ray crystallographic analysis. Its oxidation to Pd-IV complex triggers the chemoselective dyotropic rearrangement leading to the ring expansion product.

  • Details
  • Metrics
Type
research article
DOI
10.1002/anie.202211470
Web of Science ID

WOS:000884440000001

Author(s)
Gong, Jing
•
Wang, Qian
•
Zhu, Jieping  
Date Issued

2022-11-16

Publisher

Wiley-VCH Verlag GmbH

Published in
Angewandte Chemie International Edition
Volume

61

Issue

50

Article Number

e202211470

Subjects

Chemistry, Multidisciplinary

•

Chemistry

•

carbofluorination

•

chromane

•

domino process

•

dyotropic rearrangement

•

palladium

•

symmetry controlled reactions

•

cyclization-anion capture

•

c-h fluorination

•

bonds

•

fluoroarylation

•

diarylation

•

cleavage

•

esters

•

scope

Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LSPN  
Available on Infoscience
December 5, 2022
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/192928
Logo EPFL, École polytechnique fédérale de Lausanne
  • Contact
  • infoscience@epfl.ch

  • Follow us on Facebook
  • Follow us on Instagram
  • Follow us on LinkedIn
  • Follow us on X
  • Follow us on Youtube
AccessibilityLegal noticePrivacy policyCookie settingsEnd User AgreementGet helpFeedback

Infoscience is a service managed and provided by the Library and IT Services of EPFL. © EPFL, tous droits réservés