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Cross-Aldol Reaction of Isatin with Acetone Catalyzed by Leucinol: A Mechanistic Investigation
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2015 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 21, no 34, 12026-12033 p.Article in journal (Refereed) Published
Abstract [en]

Comprehensive mechanistic studies on the enantioselective aldol reaction between isatin (1a) and acetone, catalyzed by L-leucinol (3a), unraveled that isatin, apart from being a substrate, also plays an active catalytic role. Conversion of the intermediate oxazolidine 4 into the reactive syn-enamine 6, catalyzed by isatin, was identified as the rate-determining step by both the calculations (G=26.1kcalmol(-1) for the analogous L-alaninol, 3b) and the kinetic isotope effect (k(H)/k(D)=2.7 observed for the reaction using [D-6]acetone). The subsequent reaction of the syn-enamine 6 with isatin produces (S)-2a (calculated G=11.6kcalmol(-1)). The calculations suggest that the overall stereochemistry is controlled by two key events: 1)the isatin-catalyzed formation of the syn-enamine 6, which is thermodynamically favored over its anti-rotamer 7 by 2.3kcalmol(-1); and 2)the high preference of the syn-enamine 6 to produce (S)-2a on reaction with isatin (1a) rather than its enantiomer (G=2.6kcalmol(-1)).

Place, publisher, year, edition, pages
2015. Vol. 21, no 34, 12026-12033 p.
Keyword [en]
computational studies, enamines, isatins, oxazolidines, self-catalysis
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-120678DOI: 10.1002/chem.201500536ISI: 000359299700016OAI: oai:DiVA.org:su-120678DiVA: diva2:855930
Available from: 2015-09-22 Created: 2015-09-15 Last updated: 2017-12-01Bibliographically approved

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Kočovský, Pavel
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