Why do thioureas and squaramides slow down the Ireland-Claisen rearrangement?
DFT calculations
H-bonding catalysts
Ireland–Claisen rearrangement
green solvents
silyl ketene acetals
Journal
Beilstein journal of organic chemistry
ISSN: 1860-5397
Titre abrégé: Beilstein J Org Chem
Pays: Germany
ID NLM: 101250746
Informations de publication
Date de publication:
2019
2019
Historique:
received:
28
05
2019
accepted:
25
11
2019
entrez:
11
1
2020
pubmed:
11
1
2020
medline:
11
1
2020
Statut:
epublish
Résumé
A range of chiral hydrogen-bond-donating organocatalysts was tested in the Ireland-Claisen rearrangement of silyl ketene acetals. None of these organocatalysts was able to impart any enantioselectivity on the rearrangements. Furthermore, these organocatalysts slowed down the Ireland-Claisen rearrangement in comparison to an uncatalyzed reaction. The catalyst-free reaction proceeded well in green solvents or without any solvent. DFT calculations showed that the activation barriers are higher for reactions involving hydrogen-donating organocatalysts and kinetic experiments suggest that the catalysts bind stronger to the starting silyl ketene acetals than to transition structures thus leading to inefficient rearrangement reactions.
Identifiants
pubmed: 31921366
doi: 10.3762/bjoc.15.290
pmc: PMC6941421
doi:
Types de publication
Journal Article
Langues
eng
Pagination
2948-2957Informations de copyright
Copyright © 2019, Krištofíková et al.; licensee Beilstein-Institut.
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