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


ABSTRACT: 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.

SUBMITTER: Levin MD 

PROVIDER: S-EPMC5902185 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature

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A catalytic fluoride-rebound mechanism for C(sp<sup>3</sup>)-CF<sub>3</sub> bond formation.

Levin Mark D MD   Chen Tiffany Q TQ   Neubig Megan E ME   Hong Cynthia M CM   Theulier Cyril A CA   Kobylianskii Ilia J IJ   Janabi Mustafa M   O'Neil James P JP   Toste F Dean FD  

Science (New York, N.Y.) 20170601 6344


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(sp<sup>3</sup>)-CF<sub>3</sub> reductive elimination from Au(III) that accesses these compounds by a distinct mechanism proceeding via fluoride abstraction, migratory insertion, and C-F reductive elimi  ...[more]

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