Research Article

Practical olefin hydroamination with nitroarenes

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Science  22 May 2015:
Vol. 348, Issue 6237, pp. 886-891
DOI: 10.1126/science.aab0245

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Stitching C-N bonds from nitro groups

Numerous compounds in pharmaceutical research have carbon-nitrogen bonds, and chemists are always looking for ways to make them more efficiently. Gui et al. present a method that links the carbon in an olefin to the nitrogen in a nitroaromatic compound (see the Perspective by Kürti). Nitroaromatics are readily available, and the method tolerates a wide range of other chemical groups present on either reacting partner.

Science, this issue p. 886; see also p. 863

Abstract

The synthesis and functionalization of amines are fundamentally important in a vast range of chemical contexts. We present an amine synthesis that repurposes two simple feedstock building blocks: olefins and nitro(hetero)arenes. Using readily available reactants in an operationally simple procedure, the protocol smoothly yields secondary amines in a formal olefin hydroamination. Because of the presumed radical nature of the process, hindered amines can easily be accessed in a highly chemoselective transformation. A screen of more than 100 substrate combinations showcases tolerance of numerous unprotected functional groups such as alcohols, amines, and even boronic acids. This process is orthogonal to other aryl amine syntheses, such as the Buchwald-Hartwig, Ullmann, and classical amine-carbonyl reductive aminations, as it tolerates aryl halides and carbonyl compounds.

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