Direct Access to α,β‐Unsaturated γ‐Lactams via Palladium‐Catalysed Carbonylation of Propargylic Ureas

Additive carbonylations typically necessitate strong nucleophiles, such as alcohols or amines. In this study, we carbonylated a poorly nucleophilic urea, under oxidant‐free conditions. Our straightforward carbonylative strategy enables access to versatile α,β‐unsaturated γ‐lactams featuring an amino...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2024-11
Main Authors: Schiroli, Debora, Voronov, Aleksandr, Pancrazzi, Francesco, Iraci, Nunzio, Vincenzo Giofrè, Salvatore, Macchi, Beatrice, Stefanizzi, Valeria, Mancuso, Raffaella, Gabriele, Bartolo, Pio Mazzeo, Paolo, Capaldo, Luca, Della Ca', Nicola
Format: Article
Language:English
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Summary:Additive carbonylations typically necessitate strong nucleophiles, such as alcohols or amines. In this study, we carbonylated a poorly nucleophilic urea, under oxidant‐free conditions. Our straightforward carbonylative strategy enables access to versatile α,β‐unsaturated γ‐lactams featuring an aminocarbonyl fragment, utilizing readily available propargylic ureas as starting materials. The employment of the PdI 2 /KI catalytic system allowed complete regioselectivity ( 5‐endo‐dig ), high functional group tolerance, broad substrate scope as well as operational simplicity (oxidant‐free, organic ligand‐free and base‐free protocol). The synthetic utility of these γ‐lactams is showcased through late‐stage functionalizations, such as Giese reactions and peptide couplings.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.202401183