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Issue 38, 2019
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Mechanistic studies of a “Declick” reaction

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Abstract

A kinetic analysis of a “declick” reaction is described. Compound 1, previously reported to couple an amine and a thiol (i.e. “click”) under mild aqueous conditions to create 2, undergoes release of the unaltered coupling partners upon triggering with dithiothreitol (DTT). In the study reported herein various aniline derivatives possessing para-electron donating and withdrawing groups were used as the amines. UV/vis spectroscopy of the declick reaction shows time-dependent spectra lacking isosbestic points, implying a multi-step mechanism. Global data fitting using numerical integration of rate equations and singular value decomposition afforded the spectra and time-dependence of each species, as well as rate constants for each step. The kinetic analysis reveals a multi-step process with an intermediate where both thiols of DTT have added prior to expulsion of the aniline leaving group, followed by rearrangement to the final product. Hammett plots show a negative rho value on two of the steps, indicating positive charge building (i.e. reduction of a negative charge) in the step leading to the intermediate and its rate-determining breakdown. Overall, the kinetic study reported herein gives a complete mechanistic picture of the declick reaction.

Graphical abstract: Mechanistic studies of a “Declick” reaction

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Supplementary files

Article information


Submitted
08 Feb 2019
Accepted
02 Aug 2019
First published
13 Aug 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 8817-8824
Article type
Edge Article

Mechanistic studies of a “Declick” reaction

M. K. Meadows, X. Sun, I. V. Kolesnichenko, C. M. Hinson, K. A. Johnson and E. V. Anslyn, Chem. Sci., 2019, 10, 8817
DOI: 10.1039/C9SC00690G

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