Enantio- and Regioselective Copper-Catalyzed 1,2-Dearomatization of Pyridines.
Alkyne
Asymmetric Catalysis
Copper
Dearomatization
Pyridine
Stackphos
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
27 Nov 2023
27 Nov 2023
Historique:
received:
01
09
2023
medline:
11
10
2023
pubmed:
11
10
2023
entrez:
11
10
2023
Statut:
ppublish
Résumé
A copper-catalyzed dearomative alkynylation of pyridines is reported with excellent regio- and enantioselectivities. The synthetically valuable enantioenriched 2-alkynyl-1,2-dihydropyridine products afforded are generated from the readily available feedstock, pyridine, and commercially available terminal alkynes. The three-component reaction between a pyridine, a terminal alkyne, and methyl chloroformate employs copper chloride and StackPhos, a chiral biaryl P,N- ligand, as the catalytic system. Under mild reaction conditions, the desired 1,2-addition products are delivered in up to 99 % yield with regioselectivity ratios up to 25 : 1 and enantioselectivities values of up to 99 % ee. Activated and non-activated terminal alkynes containing a wide range of functional groups are well tolerated. Even acetylene gas delivered mono-alkynylated products in high yield and ee. Application of the methodology in an efficient enantioselective synthesis of the chiral piperidine indolizidine, coniceine, is reported.
Identifiants
pubmed: 37820350
doi: 10.1002/anie.202312967
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202312967Subventions
Organisme : NIH HHS
ID : S10 OD021758-01A1
Pays : United States
Organisme : NIH HHS
ID : S10 OD021758-01A1
Pays : United States
Informations de copyright
© 2023 Wiley-VCH GmbH.
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