From Prochiral N-Heterocyclic Carbenes to Optically Pure Metal Complexes New Opportunities in Asymmetric Catalysis - Archive ouverte HAL Access content directly
Journal Articles Journal of the American Chemical Society Year : 2020

From Prochiral N-Heterocyclic Carbenes to Optically Pure Metal Complexes New Opportunities in Asymmetric Catalysis

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Thomas Vives
Paola Nava

Abstract

Well-defined optically pure transition metal (TM) complexes bearing C- and C-symmetric N-heterocyclic carbene (NHC) ligands were prepared from prochiral NHC precursors. As predicted by DFT calculations, our strategy capitalizes on the formation of a metal-carbene bond which induces an axis of chirality. Configurationally stable atropisomers of various NHC-containing TM complexes were isolated by preparative HPLC on a chiral stationary phase in good yields and excellent optical purities (up to 99.5% ee). The carbene transfer from an optically pure Cu complex to a gold or palladium center reveals, for the first time, a full stereoretentivity, supporting the hypothesis of an associative mechanism for the transmetalation. The potential of these new chiral TM complexes was illustrated in asymmetric catalysis with up to 98% ee.
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Dates and versions

hal-02442228 , version 1 (24-01-2020)

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Lingyu Kong, Jennifer Morvan, Delphine Pichon, Marion Jean, Muriel Albalat, et al.. From Prochiral N-Heterocyclic Carbenes to Optically Pure Metal Complexes New Opportunities in Asymmetric Catalysis. Journal of the American Chemical Society, 2020, 142 (1), pp.93-98. ⟨10.1021/jacs.9b12698⟩. ⟨hal-02442228⟩

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