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Abadie MA, Trivelli X, Medina F, et al. Gold(I)-Catalysed Asymmetric Hydroamination of Alkenes: A Silver- and Solvent-Dependent Enantiodivergent Reaction. Chemistry. 2017;23(45):10777-10788doi: 10.1002/chem.201701301.
Abadie, M. A., Trivelli, X., Medina, F., Duhal, N., Kouach, M., Linden, B., Génin, E., Vandewalle, M., Capet, F., Roussel, P., Del Rosal, I., Maron, L., Agbossou-Niedercorn, F., & Michon, C. (2017). Gold(I)-Catalysed Asymmetric Hydroamination of Alkenes: A Silver- and Solvent-Dependent Enantiodivergent Reaction. Chemistry (Weinheim an der Bergstrasse, Germany), 23(45), 10777-10788. https://doi.org/10.1002/chem.201701301
Abadie, Marc-Antoine, et al. "Gold(I)-Catalysed Asymmetric Hydroamination of Alkenes: A Silver- and Solvent-Dependent Enantiodivergent Reaction." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 23,45 (2017): 10777-10788. doi: https://doi.org/10.1002/chem.201701301
Abadie MA, Trivelli X, Medina F, Duhal N, Kouach M, Linden B, Génin E, Vandewalle M, Capet F, Roussel P, Del Rosal I, Maron L, Agbossou-Niedercorn F, Michon C. Gold(I)-Catalysed Asymmetric Hydroamination of Alkenes: A Silver- and Solvent-Dependent Enantiodivergent Reaction. Chemistry. 2017 Aug 10;23(45):10777-10788. doi: 10.1002/chem.201701301. Epub 2017 Jun 29. PMID: 28488394.
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Chemistry. 2017 Aug 10;23(45):10777-10788. doi: 10.1002/chem.201701301. Epub 2017 Jun 29.

Gold(I)-Catalysed Asymmetric Hydroamination of Alkenes: A Silver- and Solvent-Dependent Enantiodivergent Reaction.

Chemistry (Weinheim an der Bergstrasse, Germany)

Marc-Antoine Abadie, Xavier Trivelli, Florian Medina, Nathalie Duhal, Mostafa Kouach, Bernhard Linden, Eric Génin, Maxence Vandewalle, Frédéric Capet, Pascal Roussel, Iker Del Rosal, Laurent Maron, Francine Agbossou-Niedercorn, Christophe Michon

Affiliations

  1. Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181-UCCS-Unité de Catalyse et Chimie du Solide, 59000, Lille, France.
  2. ENSCL, UCCS-CCM-MOCAH (Chimie-C7) CS 90108, 59652, Villeneuve d'Ascq Cedex, France.
  3. UGSF CNRS, UMR 8576, Université Lille Nord de France, 59655, Villeneuve d'Ascq Cedex, France.
  4. Service commun de physico-chimie CUMA, Faculté de Pharmacie-Univ. Lille, 3 rue du Professeur Laguesse BP, 83-59006, Lille Cedex, France.
  5. Linden ChroMasSpec GmbH, Auf dem Berge 25, 28844, Weyhe, Germany.
  6. ThermoFisher Scientific, 16 avenue du Québec-silic 765 Villebon-sur-Yvette, 91963, Courtaboeuf Cedex, France.
  7. Université de Toulouse et CNRS INSA, UPS, CNRS, UMR 5215, LPCNO, 135 avenue de Rangueil, 31077, Toulouse, France.

PMID: 28488394 DOI: 10.1002/chem.201701301

Abstract

In the present study, we report the first silver-dependent enantiodivergent gold-catalysed reaction. The asymmetric intramolecular hydroamination of alkenes catalysed by the combination of a single chiral binuclear gold(I) chloride complex and silver perchlorate can afford both enantiomers of the products by a simple solvent change from toluene to methanol. Such an enantiodivergent reaction is strictly independent of the reaction temperature or of the nature of the catalyst anion and displays the same first-order kinetic rate law with respect to substrate concentration in both solvents. Beyond a simple solvent effect the enantioinversion is controlled by gold-silver chloride adducts which occur only in methanol and allow a dual activation of the reagent. While one single gold atom activates the alkene moiety, the other gold atom forms an oxophilic gold-silver chloride adduct which is likely to interact with the carbamate function. By comparison with toluene, which affords (S)-enantiomer, this proximal and bimetallic activation would allow an opposite stereodifferentiation of the two diastereomeric intermediates during the final protodeauration step and lead therefore to the (R)-enantiomer.

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

Keywords: alkenes; enantiodivergent catalysis; gold; hydroamination; silver

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