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Primary Anion−π Catalysis and Autocatalysis

Frontera, Antonio
Published in Journal of the American Chemical Society. 2018, vol. 140, no. 51, p. 17867-17871
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.
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Research group Groupe Matile
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ZHANG, Xiang et al. Primary Anion−π Catalysis and Autocatalysis. In: Journal of the American Chemical Society, 2018, vol. 140, n° 51, p. 17867-17871. doi: 10.1021/jacs.8b11788 https://archive-ouverte.unige.ch/unige:112560

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Deposited on : 2019-01-07

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