American Chemical Society
ja8b11788_si_001.pdf (7.43 MB)

Primary Anion−π Catalysis and Autocatalysis

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journal contribution
posted on 2018-12-13, 20:33 authored by Xiang Zhang, Xiaoyu Hao, Le Liu, Anh-Tuan Pham, Javier López-Andarias, Antonio Frontera, Naomi Sakai, Stefan Matile
Epoxide-opening ether cyclizations are shown to occur on π-acidic aromatic surfaces without the need of additional activating groups and with autocatalytic amplification. Increasing activity with the intrinsic π acidity of benzenes, naphthalenediimides (NDIs) and perylenediimides (PDIs) support that anion−π interactions account for function. Rate enhancements maximize at 270 for anion−π catalysis on fullerenes and at 5100 M–1 for autocatalysis. The occurrence of anion−π autocatalysis is confirmed with increasing initial rates in the presence of additional product. Computational studies on autocatalysis reveal transition state and product forming a hydrogen-bonded noncovalent macrocycle, like holding their hands and dancing on the active π surface, with epoxide opening and nucleophile being activated by anion−π interactions and hydrogen bonds to the product, respectively.