Asymmetric Sequential Cu‐Catalyzed 1,6/1,4‐Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity
| Autor: | Jeanne Crassous, Sophie Colombel-Rouen, Thomas Vives, Charlie Blons, Prasad L. Polavarapu, Sean N. Cuskelly, Marie S. T. Morin, Christophe Crévisy, Craig M. Williams, Paul V. Bernhardt, Thibault E. Schmid, Olivier Baslé, Thibault Reynaldo, Hélène Gérard, Marc Mauduit, Stéphanie Halbert, Cody L. Covington |
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| Přispěvatelé: | 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 du CNRS (INC)-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 du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Queensland [Brisbane], ANR-12-BS07-0009-01, ANR (10-BLAN-724-1-NCPCHEM), ANR-10-BLAN-0724,NCPCHEM,Non-Conservation de la Parité dans les Systèmes Moléculaires(2010), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2017 |
| Předmět: |
Phosphoramidite
configuration determination [CHIM.ORGA]Chemical Sciences/Organic chemistry 010405 organic chemistry Chemistry Stereochemistry Circular Dichroism Organic Chemistry Enantioselective synthesis asymmetric catalysis conjugate addition [CHIM.CATA]Chemical Sciences/Catalysis General Chemistry 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences Nucleophile Computational chemistry Vibrational circular dichroism Optical rotatory dispersion Bimetallic strip Copper Conjugate |
| Zdroj: | Chemistry-A European Journal Chemistry-A European Journal, 2017, 23 (31), pp.7515-7525. ⟨10.1002/chem.201606034⟩ Chemistry-A European Journal, Wiley-VCH Verlag, 2017, 23 (31), pp.7515-7525. ⟨10.1002/chem.201606034⟩ |
| ISSN: | 1521-3765 0947-6539 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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