Issue 2, 2014

Organocatalytic C–H hydroxylation with Oxone® enabled by an aqueous fluoroalcohol solvent system

Abstract

Selective hydroxylation of 3° and benzylic C–H bonds is made possible using a non-metal-based catalyst system, Oxone as the terminal oxidant, and an aqueous fluoroalcohol solvent mixture. The choice of solvent is uniquely effective for this process, but seemingly at odds with our finding that H2O promotes reduction of the oxaziridine intermediate. Our studies suggest that the hydroxylation reaction is occurring within a fluoroalcohol microdroplet, which both concentrates the reactants and mitigates the deleterious impact of H2O on oxaziridine stability. These discoveries have led to demonstrable improvements in the organocatalytic oxygenation of hydrocarbon substrates and, for the first time, the successful use of Oxone with this catalyst system. Reactions generally afford product and unreacted starting material in near quantitative amounts and display outstanding selectivity for 3° and benzylic C–H bond oxidation.

Graphical abstract: Organocatalytic C–H hydroxylation with Oxone® enabled by an aqueous fluoroalcohol solvent system

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Sep 2013
Accepted
01 Nov 2013
First published
22 Nov 2013

Chem. Sci., 2014,5, 656-659

Organocatalytic C–H hydroxylation with Oxone® enabled by an aqueous fluoroalcohol solvent system

A. M. Adams and J. Du Bois, Chem. Sci., 2014, 5, 656 DOI: 10.1039/C3SC52649F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements