Design and synthesis of very strong pi-acceptor ancillary ligands. Applications in Au(I) and Pt(II) catalysis and the synthesis of natural products

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pi-acid catalysis, employing mainly Au(I) and Pt(II) based catalysts, has emerged in the last decade as one of the most efficient tools for the promotion of rearrangements in unsaturated organic substrates providing thus an exquisite entry for the synthesis of intricate skeletons that may be otherwise difficult to prepare. Herein, the employment of new ancillary ligands with enhanced pi-acceptor character is proposed as a strategy to improve the reactivity and broaden the substrate scope of some of these Au- or Pt-derived catalysts. Based in our previous findings, polycationic phosphines and also rigid phosphino-borane chelating architectures are the ligands of choice for this task. Thus, syntheses for all the new ligands as well as model reactions to ascertain their role are proposed. Finally, possible applications in the field of natural product synthesis are described.