Cross-Aldol Reaction of Isatin with Acetone Catalyzed by Leucinol: A Mechanistic Investigation

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F15%3A10312047" target="_blank" >RIV/00216208:11310/15:10312047 - isvavai.cz</a>

Alternative codes found

RIV/61388963:_____/15:00447693

Result on the web

<a href="http://dx.doi.org/10.1002/chem.201500536" target="_blank" >http://dx.doi.org/10.1002/chem.201500536</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201500536" target="_blank" >10.1002/chem.201500536</a>

Result language

angličtina

Original language name

Cross-Aldol Reaction of Isatin with Acetone Catalyzed by Leucinol: A Mechanistic Investigation

Original language description

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=2.6kcal

Czech name

—

Czech description

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Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CF - Physical chemistry and theoretical chemistry

OECD FORD branch

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Project

<a href="/en/project/GA14-31419S" target="_blank" >GA14-31419S: Computational Design of Minimalistic Metallopeptides: ‘En Route’ to Disentangling the Catalytic Power of Metalloproteins</a><br>

Continuities

S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2015

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

—

Volume of the periodical

21

Issue of the periodical within the volume

34

Country of publishing house

DE - GERMANY

Number of pages

8

Pages from-to

12026-12033

UT code for WoS article

000359299700016

EID of the result in the Scopus database

2-s2.0-84938750678