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Issue 5, 2015
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Copper-catalyzed intermolecular C(sp3)–H bond functionalization towards the synthesis of tertiary carbamates

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Abstract

We describe the development of an intermolecular unactivated C(sp3)–H bond functionalization towards the direct synthesis of tertiary carbamates. The transformation proceeded using a readily available, abundant first-row transition metal catalyst (copper), and isocyanates as the source of the amide moiety. This is a novel strategy for direct transformation of a variety of unactivated hydrocarbon feedstocks to N-alkyl-N-aryl and N,N-dialkyl carbamates without pre-functionalization or installation of a directing group. The reaction had a broad substrate scope with 3° > 2° > 1° site selectivity. The reaction proceeded even on a gram scale, and a corresponding free amine was directly obtained when the reaction was performed at high temperature. Kinetic studies suggested that radical-mediated C(sp3)–H bond cleavage was the rate-determining step.

Graphical abstract: Copper-catalyzed intermolecular C(sp3)–H bond functionalization towards the synthesis of tertiary carbamates

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Publication details

The article was received on 22 Jan 2015, accepted on 20 Mar 2015 and first published on 23 Mar 2015


Article type: Edge Article
DOI: 10.1039/C5SC00238A
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Citation: Chem. Sci., 2015,6, 3195-3200
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    Copper-catalyzed intermolecular C(sp3)–H bond functionalization towards the synthesis of tertiary carbamates

    P. K. Chikkade, Y. Kuninobu and M. Kanai, Chem. Sci., 2015, 6, 3195
    DOI: 10.1039/C5SC00238A

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