Issue 19, 2016

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

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

Supplementary files

Article information

Article type
Communication
Submitted
31 Mar 2016
Accepted
19 Apr 2016
First published
19 Apr 2016

Org. Biomol. Chem., 2016,14, 4378-4381

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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