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Title: Mechanistic study on the asymmetric synthesis of the Wieland-Miescher ketone analogs
Author: Liu, Chunhui
Bradshaw, Ben
Maseras Cuní, Feliu
Bonjoch i Sesé, Josep
Besora, Maria
Keywords: Catàlisi
Síntesi asimètrica
Asymmetric synthesis
Issue Date: 3-Jun-2019
Publisher: Wiley-VCH
Abstract: The organocatalyzed synthesis of the Wieland‐Miescher ketone (WMK) via N‐sulfonyl‐binamprolinamide catalysis was investigated using experimental and computational tools. A mechanistic proposal is presented describing the origin of the high enantioselectivity, which rivals that of aldolases. The computational study reveals that the role of the prolinamide catalyst is to lower the reaction barrier and determine the stereoselectivity of the product achieved, while the role of the carboxylic acid is to facilitate proton transfer steps. The effect of the acid co‐catalyst was confirmed by experiments. The role of the structure of the BINAM backbone and the effect of the sulfonamide group are uncovered experimentally and computationally. Calculations show that a rigid highly defined catalytic pocket due to covalent and steric interactions induces conformational changes in the triketone substrate to maximize interactions.
Note: Versió postprint del document publicat a:
It is part of: ChemCatChem, 2019, vol. 11, num. 16, p. 4064-4071
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ISSN: 1867-3880
Appears in Collections:Articles publicats en revistes (Farmacologia, Toxicologia i Química Terapèutica)

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