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Hexameric Resorcinarene Capsule is a Brønsted Acid: Investigation and Application to Synthesis and Catalysis

Author:
Zhang, Qi, Tiefenbacher, Konrad
Source:
Journal of the American Chemical Society 2013 v.135 no.43 pp. 16213-16219
ISSN:
1520-5126
Subject:
catalysts, catalytic activity, hydrogen, hydrogen bonding, hydrolysis, solvents, tertiary amines
Abstract:
Molecular capsules have attracted interest as simple enzyme mimetics and several examples of catalytic transformations in water-soluble metal–ligand based systems have been reported. This is not the case for hydrogen-bond based molecular capsules, which in contrast can be employed in organic solvents. We describe herein our investigations of such a system: The resorcin[4]arene hexamer is one of the largest hydrogen bond-based self-assembled capsules and has been studied intensively due to its ready availability. We present evidence that the capsule acts as a reasonably strong Brønsted acid (pKₐ approximately 5.5–6). This finding explains the capsule’s high affinity toward tertiary amines that are protonated and therefore encounter cation-π interactions inside the cavity. We were able to translate this finding into a first synthetic application: A highly substrate-selective Wittig reaction. We also report that this property renders the capsule an efficient enzyme-like catalyst for substrate selective diethyl acetal hydrolysis.
Agid:
5389842