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. 2019 Jan 11;10(8):2424-2428.
doi: 10.1039/c8sc04966a. eCollection 2019 Feb 28.

Aromatic C-H amination in hexafluoroisopropanol

Erica M D'Amato  1 , Jonas Börgel  2 , Tobias Ritter  1   2
Affiliations

Aromatic C-H amination in hexafluoroisopropanol

Erica M D'Amato et al. Chem Sci. .

Abstract

We report a direct radical aromatic amination reaction that provides unprotected anilines with an improvement in the substrate scope compared to prior art. Hydrogen bonding by the solvent hexafluoroisopropanol to anions of cationic species is responsible for increased reactivity and can rationalize the enhancement in substrate scope. Our findings may have bearings on radical additions to arenes for direct C-H functionalization in general.

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Figures

Fig. 1
Fig. 1. (a) [Fe]-catalyzed amination of nitrobenzene. (b). Substrate scope of this work compared to prior art. aCombined yield of isolated analytically pure individual isomers. Ratio A : B : C = 2.4 : 1.0 : 1.0. bWhile σ values cannot be used to compare reactions proceeding through different mechanisms, they do provide a semi-quantitative measure of arene electron density.
Fig. 2
Fig. 2. (a) Mechanistic hypothesis for aromatic C–H amination. (b) X-ray crystal structure of 1 crystallized from HFIP. (c) Calculated structure of 1 with explicit HFIP molecules. (d) Comparison of [Fe]-catalyzed and metal-free reactions. aStructure shown with 50% probability ellipsoids.
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