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Synthesis 2023; 55(21): 3589-3599
DOI: 10.1055/a-2018-0965
special topic
C–H Bond Functionalization of Heterocycles

Aryl Triflates in Phosphorus-Directed Rhodium(III)-Catalyzed C–H Activation

Julien Roger  ∗
,
Charline Sire
,
Anthonia Tsivery
,
Hélène Cattey 
,
Jean-Cyrille Hierso  ∗
This work was supported by the CNRS, the Université de Bourgogne, the Conseil Régional Bourgogne-Franche-Comté, and the Fonds Européen de Développement Régional (FEDER). This work was also funded by the French Agence Nationale de la Recherche via the ANR-JCJC program 2018 FIT-FUN (ANR-18-CE07-0015, for J.R. and a grant for C.S.) and the ANR PRC program 2020 CARAPH (ANR-20-CE07-0001-01, for J.-C.H).
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Abstract

Aryl triflates are selected as suitable electrophile coupling partners for the phosphorus-directed rhodium(III)-catalyzed direct C–H arylation of polyaromatic phosphines. We report herein simple conditions for the peri-C–H functionalization of polyarylphosphines, where a [Rh(III)Cl2Cp*]2 precatalyst is employed to provide a convenient access to polyarylated phosphines in up to 93% isolated yield. This synthetic approach tolerates a wide range of different aryl trifluoromethylsulfonate derivatives bearing either electron-donating (COMe, CN, CF3 or Cl) or electron-withdrawing substituents (Me, OMe) at the para-, meta- and ortho-positions, and includes bulky polyaromatic triflate substrates. We further describe access to a large class of polycyclic aromatic hydrocarbon phosphine ligands, their oxidized derivatives (i.e., their oxides and selenides), their coordination modes with Au(I) and Cu(I) coinage metal salts, and their use as efficient ligands for the atom-economic, gold-catalyzed oxidative cyclization of terminal alkynes with nitriles.

Key words

arylation - catalysis - P-ligand directed C–H activation - rhodium - trifluoromethylsulfonates - oxazoles

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2018-0965.
  • Supporting Information


Publication History

Received: 26 October 2022

Accepted after revision: 23 January 2023

Accepted Manuscript online:
23 January 2023

Article published online:
14 March 2023

© 2023. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

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