Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions

Maria Biosca, Jèssica Margalef, Xisco Caldentey, Maria Besora, Carles Rodríguez-Escrich, Joan Saltó, Xacobe C. Cambeiro, Feliu Maseras, Oscar Pàmies, Montserrat Diéguez, Miquel A. Pericàs

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12 Citations (Scopus)

Abstract

© 2018 American Chemical Society. A modular approach employing indene as common starting material, has enabled the straightforward preparation in three reaction steps of P-thioether ligands for the Pd-catalyzed asymmetric allylic substitution. The analysis of a starting library of P-thioether ligands based on rational design and theoretical calculations has led to the discovery of an optimized anthracenethiol derivative with excellent behavior in the reaction of choice. Improving most approaches reported to date, this ligand presents a broad substrate and nucleophile scope. Excellent enantioselectivities have been achieved for a range of linear and cyclic allylic substrates using a large number of C-, N-, and O-nucleophiles (40 compounds in total). The species responsible for the catalytic activity have been further investigated by NMR in order to clearly establish the origin of the enantioselectivity. The resulting products have been derivatized by means of ring-closing metathesis or Pauson-Khand reactions to further prove the synthetic versatility of the methodology for preparing enantiopure complex structures.
Original languageEnglish
Pages (from-to)3587-3601
JournalACS Catalysis
Volume8
Issue number4
DOIs
Publication statusPublished - 6 Apr 2018

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    Biosca, M., Margalef, J., Caldentey, X., Besora, M., Rodríguez-Escrich, C., Saltó, J., Cambeiro, X. C., Maseras, F., Pàmies, O., Diéguez, M., & Pericàs, M. A. (2018). Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions. ACS Catalysis, 8(4), 3587-3601. https://doi.org/10.1021/acscatal.7b04192