Asymmetric sequential Cu-catalyzed 1,6/1,4-conjugate additions of hard nucleophiles to cyclic dienones: determination of absolute configurations and origins of enantioselectivity

Blons, Charlie, Morin, Marie S. T., Schmid, Thibault E., Vives, Thomas, Colombel-Rouen, Sophie, Basle, Olivier, Reynaldo, Thibault, Covington, Cody L., Halbert, Stephanie, Cuskelly, Sean N., Bernhardt, Paul V., Williams, Craig M., Crassous, Jeanne, Polavarapu, Prasad L., Crevisy, Christophe, Gerard, Helene and Mauduit, Marc (2017) Asymmetric sequential Cu-catalyzed 1,6/1,4-conjugate additions of hard nucleophiles to cyclic dienones: determination of absolute configurations and origins of enantioselectivity. Chemistry-A European Journal, 23 31: 7515-7525. doi:10.1002/chem.201606034


Author Blons, Charlie
Morin, Marie S. T.
Schmid, Thibault E.
Vives, Thomas
Colombel-Rouen, Sophie
Basle, Olivier
Reynaldo, Thibault
Covington, Cody L.
Halbert, Stephanie
Cuskelly, Sean N.
Bernhardt, Paul V.
Williams, Craig M.
Crassous, Jeanne
Polavarapu, Prasad L.
Crevisy, Christophe
Gerard, Helene
Mauduit, Marc
Title Asymmetric sequential Cu-catalyzed 1,6/1,4-conjugate additions of hard nucleophiles to cyclic dienones: determination of absolute configurations and origins of enantioselectivity
Journal name Chemistry-A European Journal   Check publisher's open access policy
ISSN 1521-3765
0947-6539
Publication date 2017-06-01
Sub-type Article (original research)
DOI 10.1002/chem.201606034
Open Access Status Not yet assessed
Volume 23
Issue 31
Start page 7515
End page 7525
Total pages 11
Place of publication Weinheim, Germany
Publisher Wiley - V C H Verlag GmbH & Co. KGaA
Language eng
Subject 1600 Chemistry
Abstract The first stereocontrolled Cu-catalyzed sequential 1,6/1,4-asymmetric conjugate addition (ACA) of C-metalated hard nucleophiles to cyclic dienones is reported. The use of DiPPAM (diphenylphosphinoazomethinylate) followed by a phosphoramidite as the stereoinducing ligands facilitated both high ee values for the 1,6-ACA and high de values for the 1,4-ACA reaction components, which thus gave enantioenriched 1,3-dialkylated moieties. The absolute configurations were determined by using vibrational circular dichroism (VCD) and optical rotatory dispersion (ORD) spectroscopy, in combination with DFT calculations and X-ray analysis. Interestingly, DFT calculations for the mechanism of enantioselective 1,6-addition by using an unprecedented Cu–Zn bimetallic catalytic system confirmed this attribution. Lastly, exploring intramolecular cyclization avenues for enantioenriched 1,3-dialkylated products provided access to the challenging drimane skeleton.
Formatted abstract
The first stereocontrolled Cu-catalyzed sequential 1,6/1,4-asymmetric conjugate addition (ACA) of C-metalated hard nucleophiles to cyclic dienones is reported. The use of DiPPAM (diphenylphosphinoazomethinylate) followed by a phosphoramidite as the stereoinducing ligands facilitated both high ee values for the 1,6-ACA and high de values for the 1,4-ACA reaction components, which thus gave enantioenriched 1,3-dialkylated moieties. The absolute configurations were determined by using vibrational circular dichroism (VCD) and optical rotatory dispersion (ORD) spectroscopy, in combination with DFT calculations and X-ray analysis. Interestingly, DFT calculations for the mechanism of enantioselective 1,6-addition by using an unprecedented Cu–Zn bimetallic catalytic system confirmed this attribution. Lastly, exploring intramolecular cyclization avenues for enantioenriched 1,3-dialkylated products provided access to the challenging drimane skeleton.
Keyword Asymmetric catalysis
Circular dichroism
Configuration determination
Conjugate addition
Copper
Q-Index Code C1
Q-Index Status Provisional Code
Grant ID 10-BLAN-724-1-NCPCHEM
ANR-12-BS07-0009-01
CHE-0804301
FT110100851
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: HERDC Pre-Audit
School of Chemistry and Molecular Biosciences
 
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Created: Mon, 26 Jun 2017, 01:00:43 EST by Web Cron on behalf of Learning and Research Services (UQ Library)