Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, CH-1121, Geneva, Switzerland.
NCCR Molecular Systems Engineering BPR 1095, Mattenstrasse 24a, CH-4058, Basel, Switzerland.
Chemistry. 2021 Aug 19;27(47):12215-12223. doi: 10.1002/chem.202101548. Epub 2021 Jul 8.
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. Herein is reported how the broad responsiveness of ether cyclizations to diverse inputs 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.
虽然超分子原理在催化中的整合引起了越来越多的关注，但要对所得系统催化剂进行直接比较评估以得出其明显特征往往是困难的。本文报道了醚环化反应对各种输入的广泛响应如何有望填补这一空白。例如，在超分子胶囊的受限、π-碱性和 Brønsted 酸性内部进行的环化反应，以速度（远远超过一般的 Brønsted 酸和氢键催化剂）和对鲍德温规则的选择性违反（与迄今为止独特的磷属元素键合催化剂一样极端）而突出。互补的π-酸性芳香表面环化在自催化方面仍然是独特的，这表明其对类似产物的共催化剂具有化学和非对映选择性，但迄今为止不具有对映选择性。
