Lipase-Mediated Conversion of Protecting Group Silyl Ethers: An Unspecific Side Reaction.
CalB
Deprotection
Lipase
Silyl ether
TMS
Journal
Chembiochem : a European journal of chemical biology
ISSN: 1439-7633
Titre abrégé: Chembiochem
Pays: Germany
ID NLM: 100937360
Informations de publication
Date de publication:
15 09 2023
15 09 2023
Historique:
received:
23
05
2023
medline:
18
9
2023
pubmed:
24
5
2023
entrez:
24
5
2023
Statut:
ppublish
Résumé
Silyl ether protecting groups are important tools in organic synthesis, ensuring selective reactions of hydroxyl functional groups. Enantiospecific formation or cleavage could simultaneously enable the resolution of racemic mixtures and thus significantly increase the efficiency of complex synthetic pathways. Based on reports that lipases, which today are already particularly important tools in chemical synthesis, can catalyze the enantiospecific turnover of trimethylsilanol (TMS)-protected alcohols, the goal of this study was to determine the conditions under which such a catalysis occurs. Through detailed experimental and mechanistic investigation, we demonstrated that although lipases mediate the turnover of TMS-protected alcohols, this occurs independently of the known catalytic triad, as this is unable to stabilize a tetrahedral intermediate. The reaction is essentially non-specific and therefore most likely completely independent of the active site. This rules out lipases as catalysts for the resolution of racemic mixtures of alcohols through protection or deprotection with silyl groups.
Identifiants
pubmed: 37224395
doi: 10.1002/cbic.202300384
doi:
Substances chimiques
Ethers
0
Lipase
EC 3.1.1.3
Alcohols
0
Ether
0F5N573A2Y
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202300384Informations de copyright
© 2023 The Authors. ChemBioChem published by Wiley-VCH GmbH.
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