Display options
Cite
Blons C, Morin MST, Schmid TE, et al. 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. 2017;23(31):7515-7525doi: 10.1002/chem.201606034.
Blons, C., Morin, M. S. T., Schmid, T. E., Vives, T., Colombel-Rouen, S., Baslé, O., Reynaldo, T., Covington, C. L., Halbert, S., Cuskelly, S. N., Bernhardt, P. V., Williams, C. M., Crassous, J., Polavarapu, P. L., Crévisy, C., Gérard, H., & Mauduit, M. (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 (Weinheim an der Bergstrasse, Germany), 23(31), 7515-7525. https://doi.org/10.1002/chem.201606034
Blons, Charlie, et al. "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 (Weinheim an der Bergstrasse, Germany) vol. 23,31 (2017): 7515-7525. doi: https://doi.org/10.1002/chem.201606034
Blons C, Morin MST, Schmid TE, Vives T, Colombel-Rouen S, Baslé O, Reynaldo T, Covington CL, Halbert S, Cuskelly SN, Bernhardt PV, Williams CM, Crassous J, Polavarapu PL, Crévisy C, Gérard H, Mauduit M. 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. 2017 Jun 01;23(31):7515-7525. doi: 10.1002/chem.201606034. Epub 2017 May 16. PMID: 28370488.
Copy Download .nbib Format: NLM
Share it on

Chemistry. 2017 Jun 01;23(31):7515-7525. doi: 10.1002/chem.201606034. Epub 2017 May 16.

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 (Weinheim an der Bergstrasse, Germany)

Charlie Blons, Marie S T Morin, Thibault E Schmid, Thomas Vives, Sophie Colombel-Rouen, Olivier Baslé, Thibault Reynaldo, Cody L Covington, Stéphanie Halbert, Sean N Cuskelly, Paul V Bernhardt, Craig M Williams, Jeanne Crassous, Prasad L Polavarapu, Christophe Crévisy, Hélène Gérard, Marc Mauduit

Affiliations

  1. Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.
  2. Université de Rennes 1, CNRS, UMR 6226, Campus de Beaulieu, 35042, Rennes Cedex, France.
  3. Department of Chemistry, Vanderbilt University, Nashville, TN, 37235, USA.
  4. Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire de Chimie Théorique CC 137, 4, place Jussieu F., 75252, Paris Cedex 05, France.
  5. School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072, Australia.

PMID: 28370488 DOI: 10.1002/chem.201606034

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.

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: asymmetric catalysis; circular dichroism; configuration determination; conjugate addition; copper

Publication Types