Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity
In: ISSN: 0947-6539, 2017
Online
academicJournal
Zugriff:
International audience ; 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.
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Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity
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Autor/in / Beteiligte Person: | Blons, Charlie ; Morin, Marie S. T. ; Schmid, Thibault E. ; Vives, Thomas ; Colombel-Rouen, Sophie ; Baslé, Olivier ; Reynaldo, Thibault ; Covington, Cody L. ; Halbert, Stéphanie ; Cuskelly, Sean N. ; Bernhardt, Paul V. ; Williams, Craig M. ; Crassous, Jeanne ; Polavarapu, Prasad L. ; Crevisy, Christophe ; Gérard, Hélène ; Mauduit, Marc ; Institut des Sciences Chimiques de Rennes (ISCR) ; Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes) ; Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS) ; Vanderbilt University Nashville ; Laboratoire de chimie théorique (LCT) ; Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS) ; The University of Queensland (UQ All campuses : Brisbane, Dutton Park Gatton, Herston, St Lucia and other locations ) ; ANR-12-BS07-0009-01 ; (10-BLAN-724-1-NCPCHEM), ANR ; ANR-10-BLAN-0724,NCPCHEM,Non-Conservation de la Parité dans les Systèmes Moléculaires(2010) |
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Zeitschrift: | ISSN: 0947-6539, 2017 |
Veröffentlichung: | HAL CCSD ; Wiley-VCH Verlag, 2017 |
Medientyp: | academicJournal |
DOI: | 10.1002/chem.201606034 |
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