NHC-catalyzed enantioselective access to β-cyano carboxylic esters via in situ substrate alternation and release.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
12 Aug 2023
12 Aug 2023
Historique:
received:
03
04
2023
accepted:
04
08
2023
medline:
13
8
2023
pubmed:
13
8
2023
entrez:
12
8
2023
Statut:
epublish
Résumé
A carbene-catalyzed asymmetric access to chiral β-cyano carboxylic esters is disclosed. The reaction proceeds between β,β-disubstituted enals and aromatic thiols involving enantioselective protonation of enal β-carbon. Two main factors contribute to the success of this reaction. One involves in situ ultrafast addition of the aromatic thiol substrates to the carbon-carbon double bond of the enal substrate. This reaction converts almost all enal substrate to a Thiol-click Intermediate, significantly reducing aromatic thiol substrates concentration and suppressing the homo-coupling reaction of enals. Another factor is an in situ release of enal substrate from the Thiol-click Intermediate for the desired reaction to proceed effectively. The optically enriched β-cyano carboxylic esters from our method can be readily transformed to medicines that include γ-aminobutyric acids derivatives such as Rolipram. In addition to synthetic utilities, our control of reaction outcomes via in situ substrate modulation and release can likely inspire future reaction development.
Identifiants
pubmed: 37573355
doi: 10.1038/s41467-023-40645-8
pii: 10.1038/s41467-023-40645-8
pmc: PMC10423276
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
4878Subventions
Organisme : National Natural Science Foundation of China (National Science Foundation of China)
ID : 21732002
Organisme : National Natural Science Foundation of China (National Science Foundation of China)
ID : 22061007
Organisme : National Natural Science Foundation of China (National Science Foundation of China)
ID : 22071036
Organisme : National Research Foundation Singapore (National Research Foundation-Prime Minister's office, Republic of Singapore)
ID : NRF-NRFI2016-06
Organisme : National Research Foundation Singapore (National Research Foundation-Prime Minister's office, Republic of Singapore)
ID : NRF-CRP22-2019-0002
Informations de copyright
© 2023. Springer Nature Limited.
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