Mechanistic studies of a “Declick” reaction

Meadows, Margaret K.; Sun, Xiaolong; Kolesnichenko, Igor V.; Hinson, Caroline M.; Johnson, Kenneth A.; Anslyn, Eric V.

doi:10.1039/c9sc00690g

Title: Mechanistic studies of a “Declick” reaction

Journal Article · 13 August 2019 · Chemical Science

DOI: https://doi.org/10.1039/c9sc00690g · OSTI ID:1624973

Meadows, Margaret K. ^[1];

^[2];

^[3];

^[4]; Johnson, Kenneth A. ^[5];

^[4]

Mercer Univ., Macon, GA (United States). Dept. of Chemistry
Xi'an Jiaotong Univ., Shaanxi (China). The Key Lab. of Biomedical Information Engineering of Ministry of Education, School of Life Science and Technology
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Photovoltaics & Materials Technology Dept.
Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
Univ. of Texas, Austin, TX (United States). Dept. of Molecular Biosciences, Inst. for Cellular and Molecular Biology

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 ratedetermining breakdown. Overall, the kinetic study reported herein gives a complete mechanistic picture of the declick reaction.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC); Welch Regents Chair; National Science Foundation (NSF); Welch Foundation

Grant/Contract Number:: NA0003525; F-1604

OSTI ID:: 1624973

Journal Information:: Chemical Science, Vol. 10, Issue 38; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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