Issue 23, 2018

Exceptionally rapid oxime and hydrazone formation promoted by catalytic amine buffers with low toxicity

Abstract

Hydrazone and oxime bond formation between α-nucleophiles (e.g. hydrazines, alkoxy-amines) and carbonyl compounds (aldehydes and ketones) is convenient and is widely applied in multiple fields of research. While the reactants are simple, a substantial drawback is the relatively slow reaction at neutral pH. Here we describe a novel molecular strategy for accelerating these reactions, using bifunctional buffer compounds that not only control pH but also catalyze the reaction. The buffers can be employed at pH 5–9 (5–50 mM) and accelerate reactions by several orders of magnitude, yielding second-order rate constants of >10 M−1 s−1. Effective bifunctional amines include 2-(aminomethyl)imidazoles and N,N-dimethylethylenediamine. Unlike previous diaminobenzene catalysts, the new buffer amines are found to have low toxicity to human cells, and can be used to promote reactions in cellular applications.

Graphical abstract: Exceptionally rapid oxime and hydrazone formation promoted by catalytic amine buffers with low toxicity

Supplementary files

Article information

Article type
Edge Article
Submitted
06 Mar 2018
Accepted
18 May 2018
First published
21 May 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2018,9, 5252-5259

Exceptionally rapid oxime and hydrazone formation promoted by catalytic amine buffers with low toxicity

D. Larsen, A. M. Kietrys, S. A. Clark, H. S. Park, A. Ekebergh and E. T. Kool, Chem. Sci., 2018, 9, 5252 DOI: 10.1039/C8SC01082J

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, 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 commercial 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