Exploitation of Unconventional Electrophiles in Enantioselective Pd(0)-Catalyzed C–H Functionalizations

Authors

  • Daria Grosheva Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSA, BCH 4305, CH-1015 Lausanne, SCS-Metrohm Award for best oral presentation in Organic Chemistry
  • Nicolai Cramer Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSA, BCH 4305, CH-1015 Lausanne;, Email: nicolai.cramer@epfl.ch

DOI:

https://doi.org/10.2533/chimia.2019.262

Keywords:

Asymmetric catalysis, C–h functionalization, Heterocycles, Ligand design, Palladium

Abstract

Asymmetric metal-catalyzed C–H functionalization is a powerful strategy for the rapid generation of complex target molecules from simple precursors. While aryl (pseudo)halides have been used as electrophilic substrates in enantioselective Pd(0)-catalyzed syntheses of N-heterocycles, alternative partners for C–H functionalizations remain underexplored. Herein we describe the first application of ketene aminal phosphates as competent electrophiles in a Pd(0)-catalyzed desymmetrization. This transformation allowed the efficient synthesis of chiral isoindolines in a highly enantioselective fashion. Furthermore, intending to introduce sought-after perfluoroalkyl substituents, we explored intramolecular C–H functionalization of imidoyl chlorides resulting in the asymmetric preparation of previously inaccessible 1H-isoindoles. Tailored chiral monodentate ligands afforded high levels of enantioinduction in both transformations.

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Published

2019-04-24

How to Cite

[1]
D. Grosheva, N. Cramer, Chimia 2019, 73, 262, DOI: 10.2533/chimia.2019.262.