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  4. Base-Catalyzed Intramolecular Hydroamination of Cyclohexa-2,5-dienes: Insights into the Mechanism through DFT Calculations and Application to the Total Synthesis of epi-Elwesine
 
research article

Base-Catalyzed Intramolecular Hydroamination of Cyclohexa-2,5-dienes: Insights into the Mechanism through DFT Calculations and Application to the Total Synthesis of epi-Elwesine

Rousseau, Geraldine
•
Lebeuf, Raphael
•
Schenk, Kurt  
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2014
Chemistry-A European Journal

The base-catalyzed intramolecular hydroamination of 1-ethylaminocyclohexa-2,5-dienes is described. The transformation proceeds through isomerization of the cyclohexa-1,4-dienyl fragment into the corresponding conjugated 1,3-diene prior to the hydroamination step. Attaching a chiral glycinol ether auxiliary on the amino group allows the protonation to occur with complete diastereocontrol. The resulting lithium amide then adds onto the 1,3-dienyl moiety, affording the desired fused pyrrolidine ring along with the corresponding lithium allylic anion. Protonation of the latter then proceeds with high regiocontrol to favor the resulting allylic amines. In contrast, when the reaction was performed on primary amines, fused pyrrolidines bearing a homoallylic amino group were obtained. The stereochemical course of the process and determination of the reaction pathways were established based on calculations performed at the DFT level. Finally, application of the methodology to the enantioselective synthesis of (+)-epi-elwesine, a crinane alkaloid, is described.

  • Details
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Type
research article
DOI
10.1002/chem.201403662
Web of Science ID

WOS:000344358900031

Author(s)
Rousseau, Geraldine
Lebeuf, Raphael
Schenk, Kurt  
Castet, Frederic
Robert, Frederic
Landais, Yannick
Date Issued

2014

Publisher

Wiley-V C H Verlag Gmbh

Published in
Chemistry-A European Journal
Volume

20

Issue

45

Start page

14771

End page

14782

Subjects

alkaloids

•

hydroamination

•

isomerization

•

reaction mechanisms

•

rearrangements

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
IPSB  
Available on Infoscience
December 30, 2014
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/109705
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