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Issue 19, 2016
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Directing activator-assisted regio- and oxidation state-selective aerobic oxidation of secondary C(sp3)–H bonds in aliphatic alcohols

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Abstract

The regioselective conversion of an unactivated C(sp3)–H bond of a methylene carbon (CH2) into a C–O single bond is an attractive reaction in organic synthesis. Herein, we present a strategy for a regio- and oxidation state-selective aerobic C–H oxidation based on an N-hydroxyamide-derived directing activator (DA), which is attached to a hydroxy group in alcohol substrates. The DA reacts with NOx species generated in situ from NaNO2, a Brønsted acid, and aerobic oxygen, and effectively generates an amidoxyl radical from the N-hydroxy moiety of the DA. Then, the amidoxyl radical promotes site-selective intramolecular C–H abstraction from methylenes with γ- (or δ-) selectivity. The thus-generated methylene radicals are trapped by molecular oxygen and NO. This process results in the predominant formation of nitrate esters as products, which suppresses undesired overoxidation. The products can be easily converted into alcohols after hydrogenolysis.

Graphical abstract: Directing activator-assisted regio- and oxidation state-selective aerobic oxidation of secondary C(sp3)–H bonds in aliphatic alcohols

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Publication details

The article was received on 31 Mar 2016, accepted on 19 Apr 2016 and first published on 19 Apr 2016


Article type: Communication
DOI: 10.1039/C6OB00678G
Citation: Org. Biomol. Chem., 2016,14, 4378-4381
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    Directing activator-assisted regio- and oxidation state-selective aerobic oxidation of secondary C(sp3)–H bonds in aliphatic alcohols

    J. Ni, J. Ozawa, K. Oisaki and M. Kanai, Org. Biomol. Chem., 2016, 14, 4378
    DOI: 10.1039/C6OB00678G

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