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Primary Anion−π Catalysis and Autocatalysis

Author:
Zhang, Xiang, Hao, Xiaoyu, Liu, Le, Pham, Anh-Tuan, López-Andarias, Javier, Frontera, Antonio, Sakai, Naomi, Matile, Stefan
Source:
Journal of the American Chemical Society 2018 v.140 no.51 pp. 17867-17871
ISSN:
1520-5126
Subject:
Lewis bases, acidity, benzene, catalytic activity, fullerene, hydrogen bonding
Abstract:
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.
Agid:
6267645