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Fe-Catalyzed Nucleophilic Activation of C–Si versus Allylic C–O Bonds: Catalytic Trifluoromethylation of Carbonyl Groups versus Tandem Trifluormethylation–Allylation of Olefins

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Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
*E-mail for B.P.: [email protected]
Cite this: Organometallics 2014, 33, 20, 5802–5810
Publication Date (Web):July 3, 2014
https://doi.org/10.1021/om5005012
Copyright © 2014 American Chemical Society
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    Abstract

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    The nucleophilic ferrate salt Bu4N[Fe(CO)3(NO)] (TBA[Fe]) is able to catalyze the direct trifluoromethylation of aldehydes and ketones using Me3SiCF3 as a trifluoromethylating agent. Interception of the C–Si σ-bond activation using allylic acetates allows for a tandem trifluoromethylation–allylation of electron-deficient olefins. The higher activity of acetate in the C–Si bond activation and the selective Fe-catalyzed activation of the allylic acetate are prerequisites for this unprecedented three-component coupling reaction.

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    Text, figures, and tables giving general remarks, general procedures for screening reactions of the trifluoromethylation of aldehydes and ketones, solvent screening, ligand screening, general procedure for the trifluoromethylation of aldehydes and ketones, general procedure for the tandem trifluoromethylation–allylation of olefins, leaving group screening, ligand screening, adjustment of equivalents, and 1H and 13C NMR spectra of trifluoromethylated products 4–24, 29–35, 37, 38, 40, and 41. This material is available free of charge via the Internet at http://pubs.acs.org.

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