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The third orthogonal dynamic covalent bond


Lascano, Santiago; Zhang, Kang-Da; Wehlauch, Robin; Gademann, Karl; Sakai, Naomi; Matile, Stefan (2016). The third orthogonal dynamic covalent bond. Chemical Science, 7(7):4720-4724.

Abstract

Orthogonal dynamic covalent bonds are of interest for the construction of functional systems. The orthogonality of disulfide and hydrazone exchange under basic and acidic conditions, respectively, is well established. However, the integration of boronate esters as the third bond has failed so far because they exchanged too easily, especially under hydrazone exchange conditions. In this report, a collection of bioinspired catechols derived from adhesive natural products from cyanobacteria is screened with phenylboronic acids with proximal alcohols (benzoboroxoles), amines and fluorines to identify the least labile boronate esters. Moreover, Kool's 2-aminophenol catalysts are introduced to selectively accelerate hydrazone exchange without disturbing sufficiently inert boronate esters. Based on these results, we identified three different conditions to selectively exchange disulfides, hydrazones and boronate esters, that is to demonstrate the existence of three orthogonal dynamic covalent bonds. Moreover, their compatibility with functional systems is confirmed by successful hydrazone exchange in multicomponent surface architectures in the presence of intact boronate esters and disulfides.

Abstract

Orthogonal dynamic covalent bonds are of interest for the construction of functional systems. The orthogonality of disulfide and hydrazone exchange under basic and acidic conditions, respectively, is well established. However, the integration of boronate esters as the third bond has failed so far because they exchanged too easily, especially under hydrazone exchange conditions. In this report, a collection of bioinspired catechols derived from adhesive natural products from cyanobacteria is screened with phenylboronic acids with proximal alcohols (benzoboroxoles), amines and fluorines to identify the least labile boronate esters. Moreover, Kool's 2-aminophenol catalysts are introduced to selectively accelerate hydrazone exchange without disturbing sufficiently inert boronate esters. Based on these results, we identified three different conditions to selectively exchange disulfides, hydrazones and boronate esters, that is to demonstrate the existence of three orthogonal dynamic covalent bonds. Moreover, their compatibility with functional systems is confirmed by successful hydrazone exchange in multicomponent surface architectures in the presence of intact boronate esters and disulfides.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2016
Deposited On:09 Feb 2017 14:45
Last Modified:09 Feb 2017 14:56
Publisher:Royal Society of Chemistry
ISSN:2041-6520
Funders:European Research Council (ERC Advanced Investigator), Swiss National Centre of Competence in Research (NCCR) Molecular Systems Enginee
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1039/C6SC01133K

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