Publication 341

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  1. Hao, X.; Li, T.-R.; Chen, H.; Gini, A.; Zhang, X.; Rosset, S.; Mazet, C.; Tiefenbacher, K.; Matile, S. “Bioinspired Ether Cyclizations within a π-Basic Capsule Compared to Autocatalysis on π-Acidic Surfaces and Pnictogen-Bonding Catalysts” Chem. Eur. J. 2021, 27, 12215-12223

While the integration of supramolecular principles in catalysis attracts increasing attention, a direct comparative assessment of the resulting systems catalysts to work-out distinct characteristics is often difficult.  Here, we report that the broad responsiveness of ether cyclizations to diverse input promises to fill this gap.  Cyclizations in the confined, π-basic and Brønsted acidic interior of supramolecular capsules, for instance, are found to excel with speed (exceeding general Brønsted acid and hydrogen-bonding catalysts by far) and selective violations of the Baldwin rules (as extreme as the so far unique pnictogen-bonding catalysts).  The complementary cyclization on π-acidic aromatic surfaces remains unique with regard to autocatalysis, which is shown to be chemo- and diastereoselective with regard to product-like co-catalysts but, so far, not enantioselective.

DOI: 10.1002/chem.202101548 

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