Exo-selective intermolecular Diels-Alder reaction by PyrI4 and AbnU on non-natural substrates.
Journal
Communications chemistry
ISSN: 2399-3669
Titre abrégé: Commun Chem
Pays: England
ID NLM: 101725670
Informations de publication
Date de publication:
03 Aug 2021
03 Aug 2021
Historique:
received:
22
03
2021
accepted:
15
07
2021
entrez:
25
1
2023
pubmed:
3
8
2021
medline:
3
8
2021
Statut:
epublish
Résumé
The 100-year-old Diels-Alder reaction (DAr) is an atom economic and elegant organic chemistry transformation combining a 1,3-diene and a dienophile in a [4+2] cycloaddition leading to a set of products with several stereo centres and multiple stereoisomers. Stereoselective [4+2] cycloaddition is a challenge. Here, we describe two natural enzymes, PyrI4 and AbnU performing stereospecific intermolecular DAr on non-natural substrates. AbnU catalyses a single exo-stereoisomer by 32-fold higher than the background. PyrI4 catalyses the same stereoisomer (15-fold higher) as a major component (>50%). Structural, biochemical and fluorescence studies indicate that the dienophile enters first into the β-barrel of the enzymes followed by the 1,3-diene, yielding a stereospecific product. However, if some critical interactions are disrupted to increase the catalytic efficiency, stereoselectivity is compromised. Since it is established that natural enzymes can carry out intermolecular DAr on non-natural substrates, several hundreds of Diels-Alderases available in nature could be explored.
Identifiants
pubmed: 36697804
doi: 10.1038/s42004-021-00552-9
pii: 10.1038/s42004-021-00552-9
pmc: PMC9814550
doi:
Types de publication
Journal Article
Langues
eng
Pagination
113Informations de copyright
© 2021. The Author(s).
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