A catalytic fluoride-rebound mechanism for C(sp3)-CF3 bond formation

• Autores: Mark D. Levin, Tiffany Q. Chen, Megan E Neubig
• Localización: Science, ISSN 0036-8075, Vol. 356, Nº 6344, 2017, págs. 1272-1276
• Idioma: inglés
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• Resumen

  • The biological properties of trifluoromethyl compounds have led to their ubiquity in pharmaceuticals, yet their chemical properties have made their preparation a substantial challenge, necessitating innovative chemical solutions. We report the serendipitous discovery of a borane-catalyzed formal C(sp3)-CF3 reductive elimination from Au(III) that accesses these compounds by a distinct mechanism proceeding via fluoride abstraction, migratory insertion, and C-F reductive elimination to achieve a net C-C bond construction. The parent bis(trifluoromethyl)Au(III) complexes tolerate a surprising breadth of synthetic protocols, enabling the synthesis of complex organic derivatives without cleavage of the Au-C bond. This feature, combined with the “fluoride-rebound” mechanism, was translated into a protocol for the synthesis of 18F-radiolabeled aliphatic CF3-containing compounds, enabling the preparation of potential tracers for use in positron emission tomography.