Document type
ArticleVersion
Accepted versionPublication date
All rights reserved
Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/159736
Mechanistic study on the asymmetric synthesis of the Wieland-Miescher ketone analogs
Journal Title
Director/Tutor
Journal ISSN
Volume Title
Related resource
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.
Subject
Subject (English)
Citation
Citation
LIU, Chunhui, et al. Mechanistic study on the asymmetric synthesis of the Wieland-Miescher ketone analogs. ChemCatChem. 2019. Vol. 11, num. 16, pags. 4064-4071. ISSN 1867-3880. [consulted: 19 of August of 2026]. Available at: https://hdl.handle.net/2445/159736